Quinizarin compound, method for production thereof, and use therefor

ABSTRACT

This invention is to provide a novel quinizarin compound which has a quinizarin structure represented by a following formula (1) having one to four of the 5, 6, 7, and 8 positions and at least either the 6 or 7 position formed of at least one member selected from the class consisting of secondary amino groups, alkylthio groups, and optionally substituted phenylthio groups, and having the remaining positions thereof formed of at least one member selected from the class consisting of hydrogen atom, halogen atoms, amino group, hydroxy group, alkoxy groups, and optionally substituted phenoxy groups, a method for the production thereof, and a dye, an electrophotographic grade color toner composition, a thermal-transfer recording sheet, an optical recording medium, an ink jet grade ink composition and a color filter severally comprising the quinizarin compound. ##STR1##

This application is a division of application Ser. No. 08/316,244, filedSep. 30, 1994 U.S. Pat. No. 5,608,091.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel quinizarin compound, a method for theproduction thereof, a dye formed of the compound, and anelectrophotographic color toner composition, a thermal-transferrecording sheet, an optical recording medium, a color filter, and an inkjet grade ink composition severally containing the compound.

The novel quinizarin type compound of this invention exhibits absorptionin an orange-red-blue-green-near infrared region of 480 nm to 850 nm inwavelength, manifests outstanding solubility, and excels in resistanceto light or heat. In the field of optoelectronic data, the novelquinizarin type compound manifests an excellent effect as displaymaterials or recording materials exhibiting absorption in the visibleregion or near infrared region when it is used in a thermal-transferdye, an ink jet grade ink, a color separation filter for a camera tube,a liquid crystal display grade color filter, an optical color filter, acolor toner, a bar code grade ink for preventing fake, a guest-host typeliquid crystal display grade dichroic dye, a polarizer grade dichroicdye, an optical recording media suitable for compact disk, etc. Theeffect so manifested particularly gains in prominence when this compoundis used in a magenta type or cyan type dye.

Further, as a high-quality coloring agent of excellent solubility andhigh fastness fit for the orange-red-blue-green region, the quinizarintype compound of this invention manifests an ideal effect when it isused in dyes for fibers, paints for automobiles, paints for buildingmaterials, coloring agents for printing plates, writing inks, coloringagents for glass flakes, and coloring agents for spectacle lenses.

2. Description of the Prior Art

In recent years, the functionalities of the organic dye manifested inthe field of optoelectronic data recording have been attractingattention of the industry as the trend of the field toward impartationof colors to the data display images or their hard copies has beengaining in impetus. As respects the display materials or recordingmaterials suitable for this trend, the necessity for developing theso-called visible light absorption dye such as, for example, athermal-transfer dye, an ink jet grade ink, a color separation filterfor a camera tube, a liquid crystal display grade color filter, anoptical color filter, a color toner, a bar code grade ink for preventingfake, a guest-host type liquid crystal display grade dichroic dye, and apolarizer grade dichroic dye which exhibit an absorption in the visibleregion has been finding growing recognition.

Particularly, in recent years, applications which handle electronicimages including computer graphics have been suddenly increasing. As aresult, the desirability of having such electronic images as TV imagesof video movies and electronic still cameras recorded as color hardcopies has been finding growing recognition.

Among other methods which are available for the purpose of thisrecording, the so-called thermal-transfer recording method whichcomprises using a thermal transfer sheet formed by coating a substratesheet with a thermal-transfer grade dye, heating selectively the sheetwith a thermosensitive head, and transferring the molten dye onto arecording paper dyable with the molten dye has been attracting attentionas an important recording method capable of producing a full-color imageexcellent in repeatability of gradient and color.

Generally, the primary colors of yellow, magenta, and cyan are used forthese thermal transfer sheets. Very few of the dyes heretofore proposed,however, satisfy all the conditions necessary for the thermal-transferrecording, namely (1) color tone, (2) solubility in or compatibilitywith an ink solvent and an ink binder resin, (3) resistance to heat, (4)transferability, and (5) lightfastness. Thus, the appearance of a dyesatisfying the optimum conditions for the operation of thethermal-transfer recording has been longed for.

Among other compounds, the anthraquinone type compounds which areinherently stable to resist against light, heat, and temperature andexcellent in fastness have been being studied from numerous angles forthe purpose of adapting them to be controlled to an absorptionwavelength necessary for magenta dyes and cyan dyes and to be renderedsoluble in a solvent or a resin as required by intended applications.

For example, JP-A-60-122,192, JP-A-60-131,293, JP-A-60-159,091,JP-A-61-227,093, JP-A-60-253,595, JP-A-62-25,092, JP-A-62-97,886,JP-A-63-288,787, JP-A-63-288,788, JP-A-63-288,789, JP-A-01-174,490,JP-A-04-21,490, etc. disclose magenta dyes which result from introducingvarious functional groups at the 2 position into the1-amino-4-hydroxy-anthraquinone compound. Though some of them possesssolubility, they are invariably deficient in absorption wavelength orlightfastness.

Further, JP-A-59-227,948, JP-A-60-31,559, JP-A-60-53,563,JP-A-60-122,192, JP-A-60-131,292, JP-A-60-131,294, JP-A-60-151,097,JP-A-60-172,591, JP-A-61-57,391, JP-A-61-193,887, JP-A-61-255,897,JP-A-62-138,291, JP-A-01-178,495, JP-A-01-221,287, JP-A-01-255,594,JP-A-01-258,995, JP-A-01-258,996, JP-A-02-9,685, JP-A-02-43,093,JP-A-02-132,462, JP-A-02-175,293, JP-A-04-122,695, JP-A-04-270,689, etc.disclose anthraquinone type cyan dyes which have amino group, alkylaminogroup, allylamino group, and various functional groups introducedtherein. Though some of these dyes possess solubility, they areinvariably deficient in absorption wavelength or lightfastness.

The electrophotography generally produces a visible image by a procedurewhich comprises forming an electric latent image of static charge on aphotoelectroconductive sensitive material by charging or exposure tolight, then developing this electric latent image with a toner,optionally transferring the resultant toner image onto a transfer paper,and fixing the toner image by application of heat or application ofpressure. For the visible image, generally the toner which is producedby dispersing a black coloring agent such as carbon black in a binderresin is mostly used. The sudden increase of the applications which dealwith electronic images including computer graphics has been even urgingthe electromicrography to promote the impartation of colors to theelectronic images. Thus, the practice of producing color toners havingvarious dyes and/or pigments of yellow, magenta and cyan, dissolved ordispersed in a binder resin has been prevailing.

Generally, the full-color toner has been heretofore produced by meltinga binder resin and a coloring agent, kneading the molten mixture,pulverizing the resultant mixture, and classifying the produced powderand separating a powder having a prescribed grain size distribution. Inthis case, a pigment is generally used as a coloring agent. The colorimparted by the pigment is at a disadvantage in being deficient intransparency because the pigment as a coloring agent is merely dispersedin the binder resin. Particularly when an electronic image is to beformed as on a transparent sheet for use with an overhead projector, theprojected image is dim and turbid. The problem of poor transparency maybe solved to a certain extent by decreasing the grain size of thepigment particles to the order of sub-microns. The pulverization of thepigment to the order of sub-microns is difficult to attain. Further thepulverized pigment is required to be uniformly dispersed finely in thebinder resin. This uniform dispersion is extremely difficult to attain.

Numerous studies have been being continued in search of a dye whichexhibits solubility in a binder resin. The use of such a dye as acoloring agent, however, has the problem that it goes chiefly to degradethe lightfastness of the produced toner. Thus, numerous studies are nowunder way regarding the usability in the toner of a dye which exhibitshigh compatibility with a binder resin and abounds in lightfastness. Forexample, the anthraquinone type cyan dyes are disclosed inJP-A-01-237,667, JP-A-01-284,865, JP-A-02-47,668, JP-A-02-110,573,JP-A-02-132,462, JP-A-03-87,754, JP-A-05-107,812, etc. None of them,however, satisfies all the conditions of transparency, color tone, andlightfastness.

In recent years, such optical recording media as compact discs, laserdiscs, optical memory discs, and optical cards which use a semiconductorlaser as a light source have been being developed actively.Particularly, CD, PHOTO-CD, and CD-ROM are now copiously utilized asdigital recording media of high capacity and rapid access for thestorage and regeneration of voices, images, and code data. These systemsinvariably are in need of so-called near infrared absorption dyes whichare sensitive to the semiconductor laser. These dyes are desired topossess excellent characteristics.

The basic characteristics which are required of such a dye for use in anoptical recording medium include, for example, (1) that the dye iscontrolled to an absorption wavelength which is required for an intendedapplication, (2) that from the practical point of view, the dye isapplicable to a surface by a method which converts the dye into a thinfilm without using such a complicated step as vacuum deposition ordispersion in a resin, namely a method resorting as to a spin coat andenjoying convenience and excelling in productivity, and is excellent insolubility in a solvent incapable of corroding a substrate, (3) that thedye possesses high reflectance, (4) that the dye excels in resistance toheat and to light, (5) that the dye exhibits high sensitivity, and (6)that the dye as a compound excels in economy in association with aprocess for production.

Optical recording media using organic dyes which have been developed inrecent years with a view to satisfying these characteristics have beenstudied. In this respect, such organic dyes as phthalocyanine dyes,polymethine dyes, squalium dyes, and anthraquinone dyes have beenproposed. None of the dyes heretofore proposed, however, satisfies allthe characteristics mentioned above.

JP-A-58-169,152, JP-A-62-21,584, and JP-A-63-102,988, for example,disclose methods which use anthraquinone compounds as dyes. Thesecompounds, however, cannot be used practically because they areparticularly deficient in lightfastness.

The color filter is generally constructed by repeating sequentialsuperposition of fine colored picture elements in the form of thin filmstinted in a plurality of colors on a substrate such as glass, plastic,camera element, or thin-film transistor and optionally furtherdepositing a protective film thereon. Various methods have been proposedfor the formation of such colored picture elements as mentioned above.For example, photolithographic methods, printing methods,electrodeposition methods, and vacuum deposition methods have beendeveloped and adopted for practical use.

The color filters which are produced as described above are broadlydivided under those of the class using the three primary colors of red,green, and blue and those of the class using the complementary colors ofcyan, yellow, and magenta or the combination of two of thesecomplementary colors with a transparent layer. In either case, it goeswithout saying that the spectral characteristics of a given color filterdiscriminate between acceptability and rejectability of therepeatability of color of the color liquid crystal display and the colorgrade solid camera element. Attempts has been made to develop dyes,pigments, or the combinations thereof which permit production of colorfilters possessing excellent spectral characteristics.

The dyes, pigments, and combinations thereof which have been developedheretofore, however, are at a disadvantage in being deficient intransparency and lightfastness and incapable of producing desired colortones or manifesting ample repeatability.

The ink jet grade inks in many cases provide critical printcharacteristics. To be specific, water-based ink jet grade inksgenerally manifest no affinity for paper and exhibit only a poor abilityto permeate in a paper or dry in a paper. On the contrary, oil-basedinks exhibit affinity for paper and are nevertheless at a disadvantagein being deficient in surface tension and consequently liable to formunduly large ink dots and impair the print quality. In contrast thereto,solid or semi-solid type inks are characterized by being capable ofproducing prints of excellent contrast and have prospects of brightfuture. None of the dyes or pigments which are available for solid orsemi-solid type inks, however, satisfies the two factors oflightfastness and color tone at the same time.

An object of this invention, therefore, is to provide a novel quinizarincompound, a method for the production thereof, a dye formed of thecompound, and an electrographic grade color toner composition, athermal-transfer recording sheet, an optical recording medium, a colorfilter, and an ink jet grade ink composition severally containing thecompound.

Another object of this invention is to provide a novel quinizarin typecompound which is one species of anthraquinone type compounds and whichconstitutes a visible light absorption material permitting control to anabsorption wavelength fit for an intended application within the rangeof absorption wavelength from 480 to 700 nm and excelling in solubilityin a solvent or a resin used in the intended application and inlightfastness as well.

A further object of this invention is to provide a method for producingthe quinizarin type compound with high efficiency.

Still another object of this invention is to provide a dye formed of thecompound mentioned above and used as for a visible light absorptionmaterial.

Yet another object of this invention is to provide anelectrophotographic grade color toner composition which, owing to theuse of the dye possessing solubility in or miscibility with a binderresin, serves as a magenta and/or cyan color toner satisfying all thefactors of transparency, color tone, and lightfastness.

Another object of this invention is to provide a dye satisfying all theconditions of (1) color tone, (2) solubility in or compatibility with anink solvent and an ink grade binder resin, (3) resistance to heat, (4)transferability, and (5) lightfastness which are necessary for themagenta and/or cyan dye in a thermal-transfer recording sheet, and athermal-transfer recording sheet containing the dye.

Yet another object of this invention is to provide a novel opticalrecording medium, particularly a CD-oriented optical recording mediumwhich uses a laser with a wavelength of 780 nm or 680 nm, which excelsin absorption wavelength, sensitivity, reflectance, and lightfastnessowing to the use of a novel anthraquinone compound permitting control toan absorption wavelength fit for an intended application within therange of absorption wavelength of from 600 to 850 nm, excelling insolubility in a solvent such as, for example, an alcoholic solvent fitfor the intended application, and abounding in lightfastness andresistance to heat.

Another object of this invention is to provide a color filter exhibitingexcellent lightfastness, showing no turbidity, diffusing sensation oftransparency, and excelling further in terms of color tone.

Still another object of this invention is to provide an ink jet gradeink composition which permits production of prints of ideal contrast andproduction of recorded images excelling in lightfastness and in colortone as well.

SUMMARY OF THE INVENTION

The various objects mentioned above are accomplished by a quinizarincompound which has a quinizarin structure represented by a followingformula (1) having one to four of the 5, 6, 7, and 8 positions and atleast either the 6 or 7 position formed of at least one member selectedfrom the class consisting of secondary amino groups, alkylthio groups,and optionally substituted phenylthio groups, and having the remainingpositions thereof formed of at least one member selected from the classconsisting of hydrogen atom, halogen atoms, amino group, hydroxy group,alkoxy groups, and optionally substituted phenoxy groups. ##STR2##

This invention concerns the quinizarin compound, wherein one to three ofthe 5, 6, 7, and 8 positions and at least either the 6 or 7 position ofthe quinizarin structure are formed of secondary amino groups and theremaining positions thereof are formed of at least one member selectedfrom the class consisting of hydrogen atom, halogen atoms, hydroxygroup, alkoxy groups, optionally substituted phenoxy groups, alkylthiogroups, and optionally substituted phenylthio groups.

This invention also concerns the quinizarin compound, wherein at leastone of the secondary amino groups is an anilino group which may containa substituent. This invention further concerns the quinizarin compound,wherein the substituent of the anilino group is at least one memberselected from the class consisting of optionally esterified carboxylgroups, sulfonic group, cyano group, alkyl groups, alkoxy groups, andhalogen atoms. This invention further concerns the quinizarin compound,wherein the 2 and 6 positions of the anilino group are both substituted.This invention further concerns the quinizarin compound, wherein thepositions other than those formed of the secondary amino groups areformed of fluorine atoms. This invention further concerns the quinizarincompound, wherein the number of secondary amino groups is 1 or 2, thenumber of alkoxy groups or optionally substituted phenoxy groups is 1 or2, and the remaining positions are formed of fluorine atoms.

The objects are also accomplished by a magenta dye comprising thequinizarin compound containing one secondary amino group.

The objects are further accomplished by a cyan dye comprising thequinizarin compound containing two secondary amino groups.

The objects are also accomplished by an electrophotographic grade colortoner composition comprising at least one coloring agent selected fromthe group consisting of the magenta dye and the cyan dye and a binderresin.

The objects are further accomplished by a thermal-transfer recordingsheet characterized by possessing a coloring material layer containingat least one dye selected from the group consisting of the magenta dyeand the cyan dye on a substrate.

The objects are also accomplished by an optical recording medium havingthe quinizarin compound contained in a recording layer formed on asubstrate.

The objects are further accomplished by an ink jet grade ink compositioncomprising at least one dye selected from the group consisting of themagenta dye and the cyan dye and a vehicle.

This invention also concerns the ink jet grade ink composition, whereinthe vehicle contains wax.

The objects are also accomplished by a color filter containing thequinizarin compound in a filter substrate.

The objects are further accomplished by a color filter containing atleast one dye selected from the group consisting of the magenta dye andthe cyan dye in a filter substrate.

The objects are furthermore accomplished by a method for the productionof a quinizarin compound, characterized by causing a quinizarin compoundwhich has a quinizarin structure having one to four of the 5, 6, 7, and8 positions and at least either the 6 or 7 position formed of a halogenatom to react with at least one member selected from the classconsisting of primary amine compounds, aliphatic mercapto compounds,optionally substituted phenylthiols, ammonia, water, aliphatic hydroxycompounds, and optionally substituted phenols.

The objects are also accomplished by a method for the production of aquinizarin compound, characterized by causing a phthalic anhydridederivative which has a phthalic anhydride structure having one to fourof the 3, 4, 5, and 6 positions and at least either the 4 or 5 positionformed of at least one member selected from the class consisting ofsecondary amino groups, alkylthio groups, and optionally substitutedphenylthio groups and having the remaining positions formed of at leastone member selected from the class consisting of hydrogen atom, halogenatoms, amino group, hydroxy group, alkoxy groups, and optionallysubstituted phenoxy groups to react with hydroquinone or1,4-dimethoxybenzene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart showing the infrared spectrum of 6-(p-sodium sulfonateanilino)-5,7,8-trifluoroquinizarin.

EXPLANATION OF THE PREFERRED EMBODIMENT

The quinizarin compound according to this invention is a compoundrepresented by the general formula (2): ##STR3## wherein one to four ofthe W, X, Y, and Z positions and at least either the X or Y position areformed of at least one member selected from the class consisting ofsecondary amino groups, alkylthio groups, and optionally substitutedphenylthio groups and the remaining positions are formed of at least onemember selected from the class consisting of hydrogen atom, halogenatoms, amino group, hydroxy group, alkoxy groups, and optionallysubstituted phenoxy groups.

At least one of the secondary amino groups is preferably an optionallysubstituted anilino group from the viewpoint of lightfastness. Thesubstituent of the anilino group is at least one member selected fromthe class consisting of optionally esterified carboxyl groups, sulfonicgroup, cyano group, alkyl groups, alkoxy groups, and halogen atoms. Ananilino group represented by the general formula (3): ##STR4## wherein Aindependently stands for at least one member selected from the classconsisting of --COOR¹ (wherein R¹ stands for a hydrogen atom or an alkylgroup of 1 to 18, preferably 1 to 12, carbon atoms), sulfonic group,cyano group, alkyl groups of 1 to 8, preferably 1 to 6, carbon atoms,alkoxy groups of 1 to 8, preferably 1 to 6 carbon atoms, and halogenatoms, and a is an integer in the range of 0 to 5, preferably 1 to 3)may be cited as one example. In this case, the anilino group is desiredto have both the 2 and 6 positions thereof substituted with dueconsideration of solubility. In the general formula (3), the halogenatoms include, for example, a fluorine atom, a chlorine atom and abromine atom. Among other halogen atoms cited above, a fluorine atom anda chlorine atom prove to be preferable.

As another example of the secondary amino group, --NHR² (wherein R²stands for an alkyl group of 1 to 18, preferably 1 to 12, carbon atoms)may be cited.

Among the aforementioned alkyl groups, alkyl groups having 1 to 6 carbonatoms include, for example, a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, an isobutyl group, atertiary butyl group, a straight-chain or branched pentyl group, and astraight-chain or branched hexyl group. As the examples of the alkylgroup having 1 to 8 carbon atoms, in addition to the alkyl groups citedabove, a straight-chain or branched heptyl group and a straight-chain orbranched octyl group can be cited. Further, as the examples of the alkylgroup having 1 to 12 carbon atoms, in addition to the alkyl groups justcited above, a straight-chain or branched nonyl group, a straight-chainor branched decyl group, a straight-chain or branched undecyl group, anda straight-chain or -branched dodecyl group can be cited. Furthermore,as the examples of the alkyl group having 1 to 18 carbon atoms, inaddition to the alkyl groups just cited above, a straight-chain orbranched tridecyl group, a straight-chain or branched tetradecyl group,a straight-chain or branched pentadecyl group, a straight-chain orbranched hexadecyl group, a straight-chain or branched heptadecyl group,and a straight-chain or branched octadecyl group can be cited.

Among the aforementioned alkoxy groups which are contained in "A" in thegeneral formula (3), the alkoxy groups having 1 to 6 carbon atomsinclude, for example, a methoxy group, an ethoxy group, a n-propyloxygroup, an isopropyloxy group, a n-butyloxy group, an isobutyloxy group,a tertiary butyloxy group, a straight-chain or branched pentyloxy group,and a straight-chain or branched hexyloxy group. As the examples of thealkoxy group having 1 to 8 carbon atoms, in addition to the alkoxygroups cited above, a straight-chain or branched heptyloxy group, and astraight-chain or branched octyloxy group can be cited.

The alkoxy group which can be a group at a remaining position in thegeneral formula (2) is selected from among alkoxy groups having 1 to 12carbon atoms, alkoxy groups having 1 to 5 ether bonds and a total carbonnumber in the range of 2 to 12, and alkoxy groups having an alkyl groupwith a heterocycle and a total carbon number in the range of 3 to 12. Asthe examples thereof, in addition to the alkoxy groups just cited above,a straight-chain or branched pentyloxy group, a straight-chain orbranched hexyloxy group, a straight-chain or branched heptyloxy group, astraight-chain or branched octyloxy group, a straight-chain or branchednonyloxy group, a straight-chain or branched decyloxy group, astraight-chain or branched undecyloxy group, and a straight-chain orbranched dodecyloxy group, and a methoxymethoxy group, a methoxyethoxygroup, an ethoxyethoxy group, 3',6'-oxaheptyloxy group,3',6'-oxaoctyloxy group, 3',6',9'-oxadecyloxy group,3',6',9'-oxaundecyloxy group, 3',6',9',12'-oxatridecyloxy group, amethoxybutoxy group, an ethoxybutoxy group, 4',8',12'-oxatridecyloxygroup, 4',8',12',16'-oxaheptadecyloxy group, a tetrahydrofurfuryloxygroup, 4-morpholino ethoxy group and 1-piperazine ethoxy group can becited, for example.

The optionally substituted phenoxy group which can be similarly a groupat a remaining position in the general formula (2) is selected fromamong unsubstituted phenoxy groups and phenoxy groups substituted withone or two alkyl groups having 1 to 4 carbon atoms or one or two alkoxygroups having 1 to 4 carbon atoms at remaining positions of the benzenenucleus. As the examples thereof, a phenoxy group, an o-methylphenoxygroup, a m-methylphenoxy group, a p-methylphenoxy group, ano-ethylphenoxy group, a m-ethylphenoxy group, a p-ethylphenoxy group, ano-propylphenoxy group, a m-propylphenoxy group, a p-propylphenoxy group,an o-isopropylphenoxy group, a m-isopropylphenoxy group, ap-isopropylphenoxy group, an o-butylphenoxy group, a m-butylphenoxygroup, a p-butylphenoxy group, an o-tertiary butylphenoxy group, am-tertiary butylphenoxy group, a p-tertiary butylphenoxy group, ano-methoxyphenoxy group, a m-methoxyphenoxy group, a p-methoxyphenoxygroup, an o-ethoxyphenoxy group, a m-ethoxyphenoxy group, ap-ethoxyphenoxy group, an o-propioxyphenoxy group, a m-propioxyphenoxygroup, a p-propioxyphenoxy group, an o-isopropioxyphenoxy group, am-isopropioxyphenoxy group, a p-isopropioxyphenoxy group, ano-butoxyphenoxy group, a m-butoxyphenoxy group, a p-butoxyphenoxy group,a 2,6-dimethylphenoxy group, a 2,6-diethylphenoxy group, a2,6-dipropylphenoxy group, a 2,6-diisopropylphenoxy group, a2,6-dibutylphenoxy group, a 2,6-ditertiary butylphenoxy group, a2,6-dimethoxyphenoxy group, a 2,6-diethoxyphenoxy group, a2,6-dipropioxyphenoxy group, a 2,6-diisopropioxyphenoxy group, and a2,6-dibutoxyphenoxy group can be cited.

As the examples of the halogen atoms which can be similarly a group at aremaining position in the general formula (2), a fluorine atom, achlorine atom, and a bromine atom can be cited, for example. Among otherhalogen atoms cited above, a fluorine atom may be used preferably. Inparticular, by having remaining positions formed of fluorine atoms, thesolubility of the quinizarin compound in a solvent or a resin can beeffectively enhanced.

The alkylthio groups having 1 to 12 carbon atoms in the general formula(2) include, for example, a methylthio group, an ethylthio group, an-propylthio group, an isopropylthio group, a n-butylthio group, anisobutylthio group, a tertiary butylthio group, a straight-chain orbranched pentylthio group, a straight-chain or branched hexylthio group,a straight-chain or branched heptylthio group, and a straight-chain orbranched octylthio group.

Similarly, the optionally substituted phenylthio group in the generalformula (2) is an unsubstituted phenylthio group or a phenylthio groupsubstituted with one to four groups selected from the group consistingof a methyl group, a hydroxy group, a methoxy group, a carboxyl group, acyano group, a fluoro group at remaining positions of the benzenenucleus. As the examples thereof, a thiophenol group, an o-toluenethiolgroup, a m-toluenethiol group, a p-toluenethiol group, ano-hydroxythiophenol group, a m-hydroxythiophenol group, ap-hydroxythiophenol group, an o-methoxythiophenol group, am-methoxythiophenol group, a p-methoxythiophenol group, a4-carboxy-2,3,5,6-tetrafluorothiophenol group, a4-cyano-2,3,5,6-tetrafluorothiophenol group can cited.

According to this invention, a substituent which is selected among aminetype substituents of (a) type, (b) type, and (c) type and substituentsof (d) type and (e) type as specifically described below is introducedinto one or more positions of 5, 6, 7 or 8 of the structure of thequinizarin compound which is a certain kind of anthraquinone compound.

(a) type

Anilino group, o-ethoxy carbonyl anilino group, p-ethoxy carbonylanilino group, m-ethoxy carbonyl anilino group, o-butoxy carbonylanilino group, p-butoxy carbonyl anilino group, m-butoxy carbonylanilino group, o-octyloxy carbonyl anilino group, p-octyloxy carbonylanilino group, m-octyloxy carbonyl anilino group, o-octadecyloxycarbonyl anilino group, p-octadecyloxy carbonyl anilino group,m-octadecyloxy carbonyl anilino group, o-cyanoanilino group,p-cyanoanilino group, m-cyanoanilino group, o-nitroanilino group,p-nitroanilino group, m-nitroanilino group, o-methoxyanilino group,p-methoxyanilino group, m-methoxyanilino group, o-metylanilino group,p-metylanilino group, m-metylanilino group, o-tertiary butylanilinogroup, p-tertiary butylanilino group, m-tertiary butylanilino group,o-fluoroanilino group, p-fluoroanilino group, m-fluoroanilino group,2,3,5,6-tetrafluoroanilino group, 4-cyano-2,3,5,6-tetrafluoroanilinogroup, 2-methyl-4-cyanoanilino group, 2-methyl-4-nitroanilino group,2-methyl-4-carboxyanilino group, 2-methyl-4-methoxycarbonylanilinogroup, 2-butyl-4-nitroanilino group, 2-butyl-4-carboxyanilino group,2-methoxy-4-cyanoanilino group, 2-methoxy-4-nitroanilino group,2-methoxy-4-carboxyanilino group, 2-methoxy-4-methoxycarbonylanilinogroup, and 2,6-difluoroanilino group;

(b) type

2,6-Dimetylanilino group, 2,6-dietylanilino group, 2,6-dipropylanilinogroup, 2,6-diisopropylanilino group, 2,6-dibutylanilino group,2,6-diisobutylanilino group, 2,6-ditertiary butylanilino group,2,6-dihexylanilino group, 2,6-dioctylanilino group, 2,6-dimethoxyanilinogroup, 2,6-diethoxyanilino group, 2,6-dipropoxyanilino group,2,6-diisopropoxyanilino group, 2,6-dibutoxyanilino group,2,6-diisobutoxyanilino group, 2,6-ditertiary butoxyanilino group,2,6-dihexyloxyanilino group, 2,6-dioctyloxyanilino group,2,6-diethyl-3-chloroanilino group, 2,6-dichloroanilino group,2,6-dibromoanilino group, 2-methyl-6-cyanoanilino group,2-methyl-6-nitroanilino group, 2-methyl-6-carboxyanilino group,2-methyl-6-methoxycarbonylanilino group, 2-methoxy-6-methylanilinogroup, and 2-chloro-6-methylanilino group,

4-cyano-2,6-dimethylanilino group, 4-cyano-2,6-diethylanilino group,4-cyano-2,6-dipropylanilino group, 4-cyano-2,6-diisopropylanilino group,4-cyano-2,6-dibutylanilino group, 4-cyano-2,6-diisobutylanilino group,4-cyano-2,6-ditertiary butylanilino group, 4-cyano-2,6-dimethoxyanilinogroup, 4-cyano-2,6-diethoxyanilino group, 4-cyano-2,6-dipropoxyanilinogroup, 4-cyano-2,6-diisopropoxyanilino group,4-cyano-2,6-dibutoxyanilino group, 4-cyano-2,6-diisobutoxyanilino group,and 4-cyano-2,6-ditertiary butoxyanilino group,

4-nitro-2,6-dimethylanilino group, 4-nitro-2,6-diethylanilino group,4-nitro-2,6-dipropylanilino group, 4-nitro-2,6-diisopropylanilino group,4-nitro-2,6-dibutylanilino group, 4-nitro-2,6-diisobutylanilino group,4-nitro-2,6-ditertiary butylanilino group, 4-nitro-2,6-dimethoxyanilinogroup, 4-nitro-2,6-diethoxyanilino group, 4-nitro-2,6-dipropoxyanilinogroup, 4-nitro-2,6-diisopropoxyanilino group,4-nitro-2,6-dibutoxyanilino group, 4-nitro-2,6-diisobutoxyanilino group,and 4-nitro-2,6-ditertiary butoxyanilino group,

4-ethoxycarbonyl-2,6-dimethylanilino group,4-ethoxycarbonyl-2,6-diethylanilino group,4-ethoxycarbonyl-2,6-dipropylanilino group,4-ethoxycarbonyl-2,6-diisopropylanilino group,4-ethoxycarbonyl-2,6-dibutylanilino group,4-ethoxycarbonyl-2,6-diisobutylanilino group,4-ethoxycarbonyl-2,6-ditertiary butylanilino group,4-ethoxycarbonyl-2,6-dimethoxyanilino group,4-ethoxycarbonyl-2,6-diethoxyanilino group,4-ethoxycarbonyl-2,6-dipropoxyanilino group,4-ethoxycarbonyl-2,6-diisopropoxyanilino group,4-ethoxycarbonyl-2,6-dibutoxyanilino group,4-ethoxycarbonyl-2,6-diisobutoxyanilino group, and4-ethoxycarbonyl-2,6-ditertiary butoxyanilino group;

(c) type

Amino group, methyl amino group, ethyl amino group, n-propyl aminogroup, isopropyl amino group, n-butyl amino group, isobutyl amino group,tertiary butyl amino group, hexyl amino group, octyl amino group, nonylamino group, decyl amino group, dodecyl amino group, and cyclohexylaminogroup;

(d) type

Phenoxy group, o-methyl phenoxy group, m-methyl phenoxy group, p-methylphenoxy group, o-methoxy phenoxy group, m-methoxy phenoxy group, andp-methoxy phenoxy group,

methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group,n-butyloxy group, isobutyloxy group, tertiary butyloxy group, pentyloxygroup, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group,decyloxy group, and dodecyloxy group,

methoxy methoxy group, methoxy ethoxy group, ethoxy ethoxy group,3',6'-oxaheptyloxy group, 3',6'-oxaoctyloxy group, 3',6',9'-oxadecyloxygroup, 3',6',9'-oxaundecyloxy group, 3',6',9',12'-oxatridecyloxy group,methoxy butoxy group, ethoxy butoxy group, 4',8',12'-oxatridecyloxygroup, 4',8',12',16'-oxaheptadecyloxy group and tetrahydrofurfuryloxygroup;

(e) type

Methylthio group, ethylthio group, propylthio group, isopropylthiogroup, butylthio group, isobutylthio group, tertiary butylthio group,hexylthio group, octylthio group, and nonylthio group,

thiophenol group, o-toluene thiol group, m-toluene thiol group,p-toluene thiol group, o-hydroxy thiophenol group, m-hydroxy thiophenolgroup, p-hydroxy thiophenol group, o-methoxy thiophenol group, m-methoxythiophenol group, p-methoxy thiophenol group,4-carboxy-2,3,5,6-tetrafluoro thiophenol group,4-cyano-2,3,5,6-tetrafluoro thiophenol group.

The present inventors have found that the characteristics which areneeded depending on each utility aimed at as described following can beadded by introducing a substituent of type selected among theabove-mentioned (a) to (d) types into 5, 6, 7 and/or 8 position of thequinizarin structure and preferably, a fluorine atom into the remainingpositions.

To be specific, substituent(s) of (a), (b) and (c) types are mainly usedpreferably when an absorption wavelength is shifted to a longerwavelength side (b) type is particularly preferable!. In this case, thewidth of shift is varied with the kind and number of the substituent.More specifically, in the absorption wavelength in the range of 480 nmto 850 nm, it may be controlled by the kind and number of thesubstituent.

The substituent(s) of (d) type is preferably introduced into theposition(s) mainly for the purpose of remarkably improving a solubility.By the use of the substituent of such a type, a high concentration ofquinizarin compound can be dissolved in such a solvent as ketone typesolvents, e.g., acetone and methyl ethyl ketone, hydrocarbon solvents,e.g., benzene, toluene and xylene, and halogen type solvents, e.g.,chloroform and dichloroethane. With the number of substituent increased,the solubility thereof is improved.

The substituent(s) of (e) type is preferably introduced into theposition(s) for the purpose of improving a solubility, as well ascontrolling an absorption wavelength within a small range.

By introducing these substituents with any combination, the quinizarincompound can be dissolved at a high concentration in such a solvent asketone type solvents, e.g., acetone and methyl ethyl ketone, hydrocarbonsolvents, e.g., benzene, toluene and xylene, and halogen type solvents,e.g., chloroform and dichloroethane, and at the same time, theabsorption wavelength thereof can be controlled within the range of 480nm to 850 nm by the kind and number of the substituent. In particular,when a quinizarin compound having a red-type visible light range is tobe obtained, one substituent of type (a) is preferably introduced intothe positions thereof in combination with one or two substituents oftype (d), or one substituent of type (b) is preferably introducedthereinto.

When a quinizarin compound having a blue-type visible light range is tobe obtained, one substituent of type (a) and one substituent of type (c)are preferably introduced into the positions thereof in combination withone or two substituents of type (d), or two substituents of type (a) arepreferably introduced into the positions thereof in combination with oneor two substituents of type (d), or two substituents of type (b) arepreferably introduced thereinto.

When a quinizarin compound having a wavelength longer than a blue-typeone (near infrared range) is to be obtained, two or three substituentsof type (a), (b) or (c) are preferably introduced into the positionsthereof and, If necessary, in combination with one or two substituentsof type (d) or (e).

In the case of introducing substituent(s) of any of the types (a) to(e), the substituent(s) are introduced more preferably into 6 and/or 7position(s) of the quinizarin compound than into 5 and/or 8 position(s)thereof, because of the more excellent light-resistance.

The examples of the quinizarin compound of this invention may cited asfollowing.

(I) In the case of the presence of a secondary amino group at 6position.

A. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and fluorine atoms at remainingpositions:

(1) 6-anilino-5,7,8-trifluoroquinizarin,

(2) 6-(o-ethoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(3) 6-(p-ethoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(4) 6-(m-ethoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(5) 6-(o-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(6) 6-(p-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(7) 6-(m-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(8) 6-(m-octyloxycarbonylanilino)-5,7,8-trifluoroquinizarin,

(9) 6-(o-cyanoanilino)-5,7,8-trifluoroquinizarin,

(10) 6-(p-cyanoanilino)-5,7,8-trifluoroquinizarin,

(11) 6-(o-nitroanilino)-5,7,8-trifluoroquinizarin,

(12) 6-(p-nitroanilino)-5,7,8-trifluoroquinizarin,

(13) 6-(p-tertiary butylanilino)-5,7,8-trifluoroquinizarin,

(14) 6-(o-methoxylanilino)-5,7,8-trifluoroquinizarin,

(15) 6-(p-methoxylanilino)-5,7,8-trifluoroquinizarin,

(16) 6-(m-methoxylanilino)-5,7,8-trifluoroquinizarin,

(17) 6-(2,6-dimethylanilino)-5,7,8-trifluoroquinizarin,

(18) 6-(2,6-diethylanilino)-5,7,8-trifluoroquinizarin,

(19) 6-(2,6-dibutylanilino)-5,7,8-trifluoroquinizarin,

(20) 6-(2-methyl-6-nitroanilino)-5,7,8-trifluoroquinizarin,

(21) 6-(2-methyl-6-carboxyanilino)-5,7,8-trifluoroquinizarin,

(22) 6-(2,6-dichloroanilino)-5,7,8-trifluoroquinizarin,

(23) 6-(2-chloro-6-methylanilino)-5,7,8-trifluoroquinizarin,

(24) 6-(2,3,5,6-tetrafluoroanilino)-5,7,8-trifluoroquinizarin,

(25) 6-(2,6-diisopropylanilino)-5,7,8-trifluoroquinizarin,

(26) 6-(p-sulfoanilino)-5,7,8-trifluoroquinizarin,

(27) 6-(p-sodiumsulfonateanilino)-5,7,8-trifluoroquinizarin;

B. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and alkoxy groups and fluorine atoms atremaining positions:

(28) 6-anilino-7-butoxy-5,8-difluoroquinizarin,

(29) 6-(o-ethoxycarbonylanilino)-7-butoxy-5,8-difluoroquinizarin,

(30) 6-(p-ethoxycarbonylanilino)-7-butoxy-5,8-difluoroquinizarin,

(31) 6-(m-ethoxycarbonylanilino)-7-butoxy-5,8-difluoroquinizarin,

(32) 6-(o-ethoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(33) 6-(p-ethoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(34) 6-(m-ethoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(35) 6-(o-butoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(36) 6-(p-butoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(37) 6-(m-butoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(38) 6-(o-nitroanilino)-7-butoxy-5,8-difluoroquinizarin,

(39) 6-(m-nitroanilino)-7-butoxy-5,8-difluoroquinizarin,

(40) 6-(p-nitroanilino)-7-butoxy-5,8-difluoroquinizarin,

(41) 6-(p-nitroanilino)-7-octyloxy-5,8-difluoroquinizarin,

(42) 6-(o-cyanoanilino)-7-butoxy-5,8-difluoroquinizarin,

(43) 6-(m-cyanoanilino)-7-butoxy-5,8-difluoroquinizarin,

(44) 6-(p-cyanoanilino)-7-butoxy-5,8-difluoroquinizarin,

(45) 6-(p-cyanoanilino)-7-octyloxy-5,8-difluoroquinizarin,

(46) 6-(2,6-dimethylanilino)-7-methoxy-5,8-difluoroquinizarin,

(47) 6-(2,6-dimethylanilino)-7-butoxy-5,8-difluoroquinizarin,

(48) 6-(2,6-dimethylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(49) 6-(2,6-diethylanilino)-7-methoxy-5,8-difluoroquinizarin,

(50) 6-(2,6-diethylanilino)-7-butoxy-5,8-difluoroquinizarin,

(51) 6-(2,6-diethylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(52) 6-(2-nitro-6-methylanilino)-7-methoxy-5,8-difluoroquinizarin,

(53) 6-(2-nitro-6-methylanilino)-7-butoxy-5,8-difluoroquinizarin,

(54) 6-(2-nitro-6-methylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(55) 6-(2-carboxy-6-methylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(56) 6-(2,6-dichloroanilino)-7-methoxy-5,8-difluoroquinizarin,

(57) 6-(2,6-dichloroanilino)-7-butoxy-5,8-difluoroquinizarin,

(58) 6-(2,6-dichloroanilino)-7-octyloxy-5,8-difluoroquinizarin,

(59) 6-(2-chloro-6-methylanilino)-7-methoxy-5,8-difluoroquinizarin,

(60) 6-(2-chloro-6-methylanilino)-7-butoxy-5,8-difluoroquinizarin,

(61) 6-(2-chloro-6-methylanilino)-7-octyloxy-5,8-difluoroquinizarin,

(62) 6-(2,3,5,6-tetrafluoroanilino)-7-methoxy-5,8-difluoroquinizarin,

(63) 6-(2,3,5,6-tetrafluoroanilino)-7-butoxy-5,8-difluoroquinizarin,

(64) 6-(2,3,5,6-tetrafluoroanilino)-7-octyloxy-5,8-difluoroquinizarin,

(65) 6-anilino-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(66) 6-anilino-5(or 8),7-dioctyloxy-8(or 5)-fluoroquinizarin,

(67) 6-(o-ethoxycarbonylanilino)-5(or 8),7-dibutoxy-8(or5)-fluoroquinizarin,

(68) 6-(p-ethoxycarbonylanilino)-5(or 8),7-dibutoxy-8(or5)-fluoroquinizarin,

(69) 6-(m-butoxycarbonylanilino)-5(or 8),7-dibutoxy-8(or5)-fluoroquinizarin,

(70) 6-(p-butoxycarbonylanilino)-5(or 8),7-dioctyloxy-8(or5)-fluoroquinizarin,

(71) 6-(o-nitroanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(72) 6-(p-nitroanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(73) 6-(m-nitroanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(74) 6-(o-cyanoanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(75) 6-(p-cyanoanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin,

(76) 6-(m-cyanoanilino)-5(or 8),7-dibutoxy-8(or 5)-fluoroquinizarin;

C. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and hydrogen atoms at remainingpositions:

(77) 6-anilinoquinizarin,

(78) 6-(o-ethoxycarbonylanilino)quinizarin,

(79) 6-(m-ethoxycarbonylanilino)quinizarin,

(80) 6-(p-ethoxycarbonylanilino)quinizarin,

(81) 6-(o-butoxycarbonylanilino)quinizarin,

(82) 6-(m-butoxycarbonylanilino)quinizarin,

(83) 6-(p-butoxycarbonylanilino)quinizarin,

(84) 6-(o-octyloxycarbonylanilino)quinizarin,

(85) 6-(m-octyloxycarbonylanilino)quinizarin,

(86) 6-(p-octyloxycarbonylanilino)quinizarin,

(87) 6-(o-cyanoanilino)quinizarin,

(88) 6-(m-cyanoanilino)quinizarin,

(89) 6-(p-cyanoanilino)quinizarin,

(90) 6-(o-nitroanilino)quinizarin,

(91) 6-(m-nitroanilino)quinizarin,

(92) 6-(p-nitroanilino)quinizarin,

(93) 6-(o-methoxyanilino)quinizarin,

(94) 6-(m-methoxyanilino)quinizarin,

(95) 6-(p-methoxyanilino)quinizarin,

(96) 6-(2,6-dimethylanilino)quinizarin,

(97) 6-(2,6-diethylanilino)quinizarin,

(98) 6-(2,6-dipropylanilino)quinizarin,

(99) 6-(2,6-diisopropylanilino)quinizarin,

(100) 6-(2,6-dibutylanilino)quinizarin,

(101) 6-(2,6-ditertiary butylanilino)quinizarin,

(102) 6-(2,6-dichloroanilino)quinizarin,

(103) 6-(2-chloro-6-methylanilino)quinizarin,

(104) 6-(2-methyl-6-nitroanilino)quinizarin,

(105) 6-(2-methyl-6-carboxyanilino)quinizarin,

(106) 6-(2,3,4,5-tetrafluoroanilino)quinizarin;

D. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and phenoxy groups and fluorine atoms atremaining positions:

(107) 6-anilino-7-phenoxy-5,8-difluoroquinizarin,

(108) 6-(p-cyanoanilino)-7-phenoxy-5,8-difluoroquinizarin,

(109) 6-(m-ethoxycarbonylanilino)-7-phenoxy-5,8-difluoroquinizarin,

(110) 6-(2,6-dichloroanilino)-7-phenoxy-5,8-difluoroquinizarin;

E. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and alkoxy groups at remaining positions:

(111) 6-(m-ethoxycarbonylanilino)-5,7,8-tributoxyquinizarin;

F. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and phenylthio groups and fluorine atomsat remaining positions:

(112) 6-anilino-7-phenylthio-5,8-difluoroquinizarin,

(113) 6-cyanoanilino-7-phenylthio-5,8-difluoroquinizarin,

(114) 6-(2,6-dichloroanilino)-7-phenylthio-5,8-difluoroquinizarin,

(115) 6-(m-ethoxycarbonyl)-7-phenylthio-5,8-difluoroquinizarin;

G. Examples of the quinizarin compound having one secondary amino group(alkylamino group) at 6 position, and fluorine atoms at remainingpositions:

(116) 6-ethylamino-5,7,8-trifluoroquinizarin,

(117) 6-butylamino-5,7,8-trifluoroquinizarin,

(118) 6-octylamino-5,7,8-trifluoroquinizarin,

(119) 6-cyclohexylamino-5,7,8-trifluoroquinizarin;

H. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and fluorine atoms at remainingpositions:

(120) 6,7-dianilino-5,8-difluoroquinizarin,

(121) 6,7-bis(m-ethoxycarbonylanilino)-5,8-difluoroquinizarin,

(122) 6,7-bis(o-butoxycarbonylanilino)-5,8-difluoroquinizarin,

(123) 6,7-bis(p-butoxycarbonylanilino)-5,8-difluoroquinizarin,

(124) 6,7-bis(m-butoxycarbonylanilino)-5,8-difluoroquinizarin,

(125) 6,7-bis(o-cyanoanilino)-5,8-difluoroquinizarin,

(126) 6,7-bis(p-cyanoanilino)-5,8-difluoroquinizarin,

(127) 6,7-bis(o-nitroanilino)-5,8-difluoroquinizarin,

(128) 6,7-bis(p-nitroanilino)-5,8-difluoroquinizarin,

(129) 6,7-bis(o-tertiary butylanilino)-5,8-difluoroquinizarin,

(130) 6,7-bis(p-tertiary butylanilino)-5,8-difluoroquinizarin,

(131) 6,7-bis(o-methoxyanilino)-5,8-difluoroquinizarin,

(132) 6,7-bis(p-methoxyanilino)-5,8-difluoroquinizarin,

(133) 6,7-bis(m-methoxyanilino)-5,8-difluoroquinizarin,

(134) 6,7-bis(2,6-dibutylanilino)-5,8-difluoroquinizarin,

(135) 6,7-bis(2,6-difluoroanilino)-5,8-difluoroquinizarin,

(136) 6,7-bis(2,6-dimetylanilino)-5,8-difluoroquinizarin,

(137) 6,7-bis(2,6-dietylanilino)-5,8-difluoroquinizarin,

(138) 6,7-bis(2,6-dichloroanilino)-5,8-difluoroquinizarin,

(139) 6,7-bis(2,6-diisopropylanilino)-5,8-difluoroquinizarin,

(140) 6,7-bis(2,6-dibromoanilino)-5,8-difluoroquinizarin,

(141) 6,7-bis(2,6-diethyl-3-chloroanilino)-5,8-difluoroquinizarin,

(142) 6,7-bis(2-methoxy-6-methylanilino)-5,8-difluoroquinizarin,

(143) 6,7-bis(2-chloro-6-methylanilino)-5,8-difluoroquinizarin,

(144) 6,7-bis(2-ethoxycarbonyl-6-methylanilino)-5,8-difluoroquinizarin,

(145) 6,7-bis(2,3,5,6-tetrafluoroanilino)-5,8-difluoroquinizarin,

(146) 6,7-bis(2-chloro-6-methylanilino)-5,8-difluoroquinizarin,

(147) 6,7-bis(o-octyloxycarbonylanilino)-5,8-difluoroquinizarin,

(148) 6,7-bis(o-octadecyloxycarbonylanilino)-5,8-difluoroquinizarin,

(149) 6,7-bis(4-ethoxy-2,6-dipropylanilino)-5,8-difluoroquinizarin,

(150)6,7-bis(4-methoxyethoxy-2,6-diisopropylanilino)-5,8-difluoroquinizarin,

(151) 6,7-bis(4-hydroxy-2,6-dibutylanilino)-5,8-difluoroquinizarin,

(152) 6,7-bis(2-ethoxy-6-methylanilino)-5,8-difluoroquinizarin,

(153) 6,7-bis(2,6-diethoxyanilino)-5,8-difluoroquinizarin;

I. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and alkoxy groups and fluorineatoms at remaining positions:

(154) 6,7-dianilino-5-butoxy-8-fluoroquinizarin,

(155) 6,7-dianilino-5-octyloxy-8-fluoroquinizarin,

(156) 6,7-bis(m-ethoxycarbonylanilino)-5-octyloxy-8-fluoroquinizarin,

(157) 6,7-bis(p-ethoxycarbonylanilino)-5-octyloxy-8-fluoroquinizarin,

(158) 6,7-bis(2,6-diethylanilino)-5-butoxy-8-fluoroquinizarin,

(159) 6,7-bis(2,6-diisopropylanilino)-5-butoxy-8-fluoroquinizarin,

(160) 6,7-bis(2,6-diethyl-3-chloroanilino)-5-butoxy-8-fluoroquinizarin,

(161)6,7-bis(2,6-diethyl-3-chloroanilino)-5-octyloxy-8-fluoroquinizarin,

(162)6,7-bis(2-ethoxycarbony-6-methylanilino)-5-butoxy-8-fluoroquinizarin,

(163)6,7-bis(2-ethoxycarbony-6-methylanilino)-5-octyloxy-8-fluoroquinizarin,

(164) 6,7-bis(2,6-dimethylanilino)-5-octyloxy-8-fluoroquinizarin,

(165) 6,7-bis(2,6-diethylanilino)-5-octyloxy-8-fluoroquinizarin,

(166) 6,7-bis(o-ethoxyanilino)-5-butoxy-8-fluoroquinizarin,

(167) 6,7-bis(p-ethoxyanilino)-5-butoxy-8-fluoroquinizarin,

(168) 6,7-bis(p-ethoxyanilino)-5-ethoxyethoxy-8-fluoroquinizarin,

(169) 6,7-bis(o-ethoxyanilino)-5-octyloxy-8-fluoroquinizarin,

(170) 6,7-bis(p-methoxyethoxyanilino)-5-octyloxy-8-fluoroquinizarin,

(171) 6,7-bis(p-ethoxyethoxyanilino)-5-ethoxyethoxy-8-fluoroquinizarin,

(172)6,7-bis(o-butoxyanilino)-5-(p-3',6',9'-oxahendecyloxy)-8-fluoroquinizarin,

(173) 6,7-bis(p-butoxyanilino)-5-ethoxyethoxy-8-fluoroquinizarin,

(174) 6,7-bis(p-hydroxyanilino)-5-butoxy-8-fluoroquinizarin,

(175) 6,7-bis(o-butylanilino)-5-octyloxy-8-fluoroquinizarin,

(176) 6,7-bis(p-octyloxyanilino)-5-octyloxy-8-fluoroquinizarin,

(177)6,7-bis(p-3',6',9'-oxahendecyloxyanilino)-5-octyloxy-8-fluoroquinizarin,

(178) 6,7-bis(2,6-dipropylanilino)-5-butoxy-8-fluoroquinizarin,

(179) 6,7-bis(2,6-dibutylanilino)-5-butoxy-8-fluoroquinizarin,

(180)6,7-bis(2,6-diisopropylanilino)-5-methoxyethoxy-8-fluoroquinizarin,

(181) 6,7-bis(2,6-difluoroanilino)-5-octyloxy-8-fluoroquinizarin,

(182) 6,7-bis(2,6-dichloroanilino)-5-butoxy-8-fluoroquinizarin,

(183) 6,7-bis(2,6-dichloroanilino)-5-octyloxy-8-fluoroquinizarin,

(184) 6,7-bis(2,6-dibromoanilino)-5-butoxy-8-fluoroquinizarin,

(185) 6,7-bis(2,6-dibromoanilino)-5-octyloxy-8-fluoroquinizarin,

(186) 6,7-bis(2-methoxy-6-methylanilino)-5-butoxy-8-fluoroquinizarin,

(187) 6,7-bis(2-methoxy-6-methylanilino)-5-octyloxy-8-fluoroquinizarin,

(188) 6,7-bis(2-chloro-6-methylanilino)-5-butoxy-8-fluoroquinizarin,

(189) 6,7-bis(2-chloro-6-methylanilino)-5-octyloxy-8-fluoroquinizarin,

(190) 6,7-bis(2-ethoxy-6-methylanilino)-5-butoxy-8-fluoroquinizarin,

(191) 6,7-bis(2-ethoxy-6-methylanilino)-5-octyloxy-8-fluoroquinizarin;

J. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, and alkoxygroups and fluorine atoms at remaining positions:

(192) 6-anilino-7-ethylamino-5(or 8)-octyloxy-8(or 5)-fluoroquinizarin,

(193) 6-anilino-7-butylamino-8(or 5)-octyloxy-5(or 8)-fluoroquinizarin,

(194) 6-(m-ethoxycarbonylanilino)-7-butylamino-5(or 8)-butoxy-8(or5)-fluoroquinizarin,

(195) 6-(o-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(196) 6-(p-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(197) 6-(m-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(198) 6-(o-cyanoanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(199) 6-(p-cyanoanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(200) 6-(m-cyanoanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(201) 6-(o-nitroanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(202) 6-(p-nitroanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(203) 6-(m-nitroanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin,

(204) 6-anilino-7-butylamino-5(or 8)-butoxy-8(or 5)-fluoroquinizarin,

(205) 6-(o-ethoxyanilino)-7-butylamino-5(or 8)-butyloxy-8(or5)-fluoroquinizarin,

(206) 6-(o-butoxyanilino)-7-butylamino-5(or 8)-butyloxy-8(or5)-fluoroquinizarin,

(207) 6-(p-ethoxyanilino)-7-butylamino-5(or 8)-butyloxy-8(or5)-fluoroquinizarin,

(208) 6-(o-ethoxyanilino)-7-butylamino-5(or 8)-octyloxy-8(or5)-fluoroquinizarin,

(209) 6-(o-ethoxyanilino)-7-butylamino-5(or 8)-methoxyethoxy-8(or5)-fluoroquinizarin,

(210) 6-(p-ethoxyanilino)-7-butylamino-5(or 8)-ethoxyethoxy-8(or5)-fluoroquinizarin,

(211) 6-(o-methoxyethoxyanilino)-7-butylamino-5(or 8)-butyloxy-8(or5)-fluoroquinizarin,

(212) 6-(p-ethoxyethoxyanilino)-7-butylamino-5(or 8)-methoxymethoxy-8(or5)-fluoroquinizarin,

(213) 6-(p-butoxyanilino)-7-butylamino-5(or8)-3',6',9'-oxahendecyloxy-8(or 5)-fluoroquinizarin,

(214) 6-(o-butoxyanilino)-7-butylamino-5(or 8)-octyloxy-8(or5)-fluoroquinizarin,

(215) 6-(p-butoxyanilino)-7-butylamino-5(or 8)-phenyloxy-8(or5)-fluoroquinizarin,

(216) 6-(p-butoxyanilino)-7-butylamino-5(or 8)-octyloxy-8(or5)-fluoroquinizarin;

K. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, and alkoxygroups at remaining positions:

(217) 6-anilino-7-butylamino-5,8-dibutoxyquinizarin,

(218) 6-(o-ethoxycarbonylanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(219) 6-(p-ethoxycarbonylanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(220) 6-(m-ethoxycarbonylanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(221) 6-(o-cyanoanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(222) 6-(p-cyanoanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(223) 6-(m-cyanoanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(224) 6-(o-nitroanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(225) 6-(p-nitroanilino)-7-butylamino-5,8-dibutoxyquinizarin,

(226) 6-(m-nitroanilino)-7-butylamino-5,8-dibutoxyquinizarin;

L. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, andfluorine atoms at remaining positions:

(227) 6-(m-ethoxycarbonylanilino)-7-butylamino-5,8-difluoroquinizarin,

(228) 6-(p-methoxyanilino)-7-butylamino-5,8-difluoroquinizarin,

(229) 6-anilino-7-butylamino-5,8-difluoroquinizarin;

M. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and hydroxy groups and fluorineatoms at remaining positions:

(230) 6,8(or 5)-bis(2,6-dichloroanilino)-7-hydroxy-5(or8)-fluoroquinizarin,

(231) 6,8(or 5)-bis(2,6-diisopropylanilino)-7-hydroxy-5(or8)-fluoroquinizarin;

N. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and either alkylthio groups orphenylthio groups and fluorine atoms at remaining positions:

(232) 6,7-bis(2,6-diisopropylanilino)-5-octylthio-8-fluoroquinizarin,

(233) 6,7-bis(2,6-diethoxyanilino)-5-octylthio-8-fluoroquinizarin,

(234) 6,7-bis(2,6-diethoxyanilino)-5-phenylthio-8-fluoroquinizarin;

O. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and either alkylthio groups orphenylthio groups at remaining positions:

(235) 6,7-bis(2,6-diethylanilino)-5,8-dibutylthioquinizarin,

(236) 6,7-bis(2,6-diisopropylanilino)-5,8-dibutylthioquinizarin,

(237) 6,7-bis(2,6-diisopropylanilino)-5,8-diphenylthioquinizarin,

(238)6,7-bis(2,6-diisopropyl-4-ethoxyanilino)-5,8-dibutylthioquinizarin;

P. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, and eitheralkylthio groups or phenylthio groups and fluorine atoms at remainingpositions:

(239)6-(2,6-diisopropylanilino)-7-butylamino-5-octylthio-8-fluoroquinizarin,

(240)6-(2,6-diethoxyanilino)-7-butylamino-5-octylthio-8-fluoroquinizarin,

(241)6-(2,6-diethoxyanilino)-7-butylamino-5-phenylthio-8-fluoroquinizarin;

Q. Examples of the quinizarin compound having two secondary amino groups(alkylamino groups) at at least 6 position, and fluorine atoms atremaining positions:

(242) 6,7-dibutylamino-5,8-difluoroquinizarin;

R. Examples of the quinizarin compound having three secondary aminogroups (anilino groups) at at least 6 position, and fluorine atoms atremaining positions:

(243) 5,6,7-tris(2,6-diethylanilino)-8-fluoroquinizarin,

(244) 5,6,7-tris(2,6-dipropylanilino)-8-fluoroquinizarin,

(245) 5,6,7-tris(2,6-diisopropylanilino)-8-fluoroquinizarin,

(246) 5,6,7-tris(2-chloro-6-methylanilino)-8-fluoroquinizarin,

(247) 5,6,7-tris(2,6-diethoxyanilino)-8-fluoroquinizarin;

S. Examples of the quinizarin compound having three secondary aminogroups (anilino group and alkylamino group) at at least 6 position, andfluorine atoms at remaining positions:

(248) 5,6,7-tris(butylamino)-8-fluoroquinizarin,

(249)5,6-bis(2,6-diisobutylpropylanilino)-7-butylamino-8-fluoroquinizarin,

(250) 5,6-bis(2,6-diisopropylanilino)-7-octylamino-8-fluoroquinizarin,

(251) 5,6-bis(2,6-diethoxyanilino)-7-butylamino-8-fluoroquinizarin,

(252) 5,6-bis(2,6-diethoxyanilino)-7-octylamino-8-fluoroquinizarin;

T. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and chlorine atoms at remainingpositions:

(253) 6-(m-ethoxycarbonylanilino)-5,7,8-trichloroquinizarin,

(254) 6-(2,6-dimethylanilino)-5,7,8-trichloroquinizarin,

(255) 6-(2,6-diethylanilino)-5,7,8-trichloroquinizarin,

(256) 6-(2-methyl-6-carboxyanilino)-5,7,8-trichloroquinizarin,

(257) 6-(2,6-dichloroanilino)-5,7,8-trichloroquinizarin,

(258) 6-(2,6-diisopropylanilino)-5,7,8-trichloroquinizarin;

U. Examples of the quinizarin compound having one secondary amino group(anilino group) at 6 position, and alkoxy groups and chlorine atoms atremaining positions:

(259) 6-(m-ethoxycarbonylanilino)-7-octyloxy-5,8-dichloroquinizarin,

(260) 6-(p-butoxycarbonylanilino)-7-octyloxy-5,8-dichloroquinizarin,

(261) 6-(p-nitroanilino)-7-octyloxy-5,8-dichloroquinizarin,

(262) 6-(p-cyanoanilino)-7-octyloxy-5,8-dichloroquinizarin,

(263) 6-anilino-5(or 8),7-dibutoxy-8(or 5)-chloroquinizarin,

(264) 6-(m-ethoxycarbonylanilino)-5(or 8),7-dibutoxy-8(or5)-chloroquinizarin,

(265) 6-(p-butoxycarbonylanilino)-5(or 8),7-dibutoxy-8(or5)-chloroquinizarin,

(266) 6-(p-nitroanilino)-5(or 8),7-dibutoxy-8(or 5)-chloroquinizarin,

(267) 6-(p-cyanoanilino)-5(or 8),7-dibutoxy-8(or 5)-chloroquinizarin;

V. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and chlorine atoms at remainingpositions:

(268) 6,7-bis(2,6-diethylanilino)-5,8-dichloroquinizarin,

(269) 6,7-bis(2,6-diisopropylanilino)-5,8-dichloroquinizarin;

W. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and alkoxy groups and chlorineatoms at remaining positions:

(270) 6,7-bis(m-ethoxycarbonylanilino)-5-octyloxy-8-chloroquinizarin,

(271) 6,7-bis(p-ethoxycarbonylanilino)-5-octyloxy-8-chloroquinizarin,

(272) 6,7-bis(2,6-diethylanilino)-5-butoxy-8-chloroquinizarin,

(273) 6,7-bis(2,6-diisopropylanilino)-5-butoxy-8-chloroquinizarin,

(274) 6,7-bis(2,6-diethyl-3-chloroanilino)-5-butoxy-8-chloroquinizarin,

(275)6,7-bis(2,6-diethyl-3-chloroanilino)-5-octyloxy-8-chloroquinizarin,

(276)6,7-bis(2-ethoxycarbony-6-methylanilino)-5-butoxy-8-chloroquinizarin,

(277)6,7-bis(2-ethoxycarbony-6-methylanilino)-5-octyloxy-8-chloroquinizarin;

X. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, and alkoxygroups and chlorine atoms at remaining positions:

(278) 6-anilino-7-butylamino-8(or 5)-octyloxy-5(or 8)-chloroquinizarin,

(279) 6-(m-ethoxycarbonylanilino)-7-butylamino-5(or 8)-butoxy-8(or5)-chloroquinizarin,

(280) 6-(p-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or⁸)-chloroquinizarin,

(281) 6-(m-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-chloroquinizarin;

Y. Examples of the quinizarin compound having two secondary amino groups(anilino group and alkylamino group) at at least 6 position, and alkoxygroups and hydrogen atoms at remaining positions:

(282) 6-anilino-7-butylamino-8(or 5)-octyloxyquinizarin,

(283) 6-(m-ethoxycarbonylanilino)-7-butylamino-5(or 8)-butoxyquinizarin,

(284) 6-(p-ethoxycarbonylanilino)-7-butylamino-8(or5)-octyloxyquinizarin,

(285) 6-(m-ethoxycarbonylanilino)-7-butylamino-8(or5)-octyloxyquinizarin;

Z. Examples of the quinizarin compound having two secondary amino groups(anilino groups) at at least 6 position, and alkoxy groups and hydrogenatoms at remaining positions:

(286) 6,7-bis(m-ethoxycarbonylanilino)-5-octyloxyquinizarin,

(287) 6,7-bis(p-ethoxycarbonylanilino)-5-octyloxyquinizarin,

(288) 6,7-bis(2,6-diethylanilino)-5-butoxyquinizarin,

(289) 6,7-bis(2,6-diisopropylanilino)-5-butoxyquinizarin,

(290) 6,7-bis(2,6-diethy-3-chloroanilino)-5-butoxyquinizarin,

(291) 6,7-bis(2,6-diethyl-3-chloroanilino)-5-octyloxyquinizarin,

(292) 6,7-bis(2-ethoxycarbonyl-6-methylanilino)-5-butoxyquinizarin,

(293) 6,7-bis(2-ethoxycarbonyl-6-methylanilino)-5-octyloxyquinizarin,

(294) 6,7-bis(2,6-diethylanilino)quinizarin,

(295) 6,7-bis(2,6-diisopropylanilino)quinizarin;

1! Examples of the quinizarin compound having two phenylthio groups andone amino group, and fluorine atoms at remaining positions:

(296) 5-amino-6,7-diphenylthio-8-fluoroquinizarin;

2! Examples of the quinizarin compound having two phenylthio groups at 6and 7 positions, and two anilino groups at remaining positions:

(297) 5,8-dianilino-6,7-diphenylthioquinizarin;

3! Examples of the quinizarin compound having two phenylthio groups, andfluorine atoms at remaining positions:

(298) 6,7-diphenylthio-5,8-difluoroquinizarin,

(299)6,7-bis(4-carboxy-2,3,5,6-tetrafluorophenylthio)-5,8-difluoroquinizarin,

(300)6,7-bis(4-cyano-2,3,5,6-tetrafluorophenylthio)-5,8-difluoroquinizarin,

(301) 6,7-bis(p-hydroxyphenylthio)-5,8-difluoroquinizarin,

(302) 6,7-bis(p-methoxyphenylthio)-5,8-difluoroquinizarin;

4! Examples of the quinizarin compound having two alkylthio groups, andfluorine atoms at remaining positions:

(303) 6,7-dihexylthio-5,8-difluoroquinizarin,

(304) 6,7-dioctylthio-5,8-difluoroquinizarin,

(305) 6,7-ditertiary butylthio-5,8-difluoroquinizarin,

(306) 6,7-dicyclohexylthio-5,8-difluoroquinizarin;

5! Examples of the quinizarin compound having four phenylthio groups:

(307) 5,6,7,8-tetraphenylthioquinizarin;

6! Examples of the quinizarin compound having four alkylthio groups:

(308) 5,6,7,8-tetrabutylthioquinizarin;

7! Examples of the quinizarin compound having two phenylthio groups andone amino group, and chlorine atoms at remaining positions:

(309) 5-amino-6,7-diphenylthio-8-chloroquinizarin;

8! Examples of the quinizarin compound having two phenylthio groups, andchlorine atoms at remaining positions:

(310) 6,7-diphenylthio-5,8-dichloroquinizarin,

(311)6,7-bis(4-carboxy-2,3,5,6-tetrafluorophenylthio)-5,8-dichloroquinizarin,

(312)6,7-bis(4-cyano-2,3,5,6-tetrafluorophenylthio)-5,8-dichloroquinizarin,

(313) 6,7-bis(p-hydroxyphenylthio)-5,8-dichloroquinizarin,

(314) 6,7-bis(p-methoxyphenylthio)-5,8-dichloroquinizarin;

9! Examples of the quinizarin compound having two alkylthio groups, andchlorine atoms at remaining positions:

(315) 6,7-dihexylthio-5,8-dichloroquinizarin,

(316) 6,7-dioctylthio-5,8-dichloroquinizarin,

(317) 6,7-ditertiary butylthio-5,8-dichloroquinizarin,

(318) 6,7-dicyclohexylthio-5,8-dichloroquinizarin;

10! Examples of the quinizarin compound having two phenylthio groups andone amino group, and hydrogen atoms at remaining positions:

(319) 5-amino-6,7-diphenylthioquinizarin;

11! Examples of the quinizarin compound having two phenylthio groups,and hydrogen atoms at remaining positions:

(320) 6,7-diphenylthioquinizarin,

(321) 6,7-bis(4-carboxy-2,3,5,6-tetrafluorophenylthio)quinizarin,

(322) 6,7-bis(4-cyano-2,3,5,6-tetrafluorophenylthio)quinizarin,

(323) 6,7-bis(p-hydroxyphenylthio)-5,8-quinizarin,

(324) 6,7-bis(p-methoxyphenylthio)-5,8-quinizarin;

12! Examples of the quinizarin compound having two alkylthio groups, andhydrogen atoms at remaining positions:

(325) 6,7-dihexylthioquinizarin,

(326) 6,7-dioctylthioquinizarin,

(327) 6,7-ditertiary butylthioquinizarin,

(328) 6,7-dicyclohexylthioquinizarin.

The novel quinizarin compound of this invention can be produced by thetwo methods described above, for example. One of the methods ofproduction comprises preparing as a starting material a quinizarinhaving the 5, 6, 7 and 8 positions, or the 5, 6 and 7 positions, or the5, 6 and 8 positions, or the 5 and 6 positions, or the 5 and 7positions, or the 6 and 7 positions, or the 6 position, or the 7position thereof substituted with halogen atoms as represented by thefollowing general formula (4): ##STR5## (wherein R⁰ stands for a halogenatom and n is an integer in the range of 0 to 3)

and causing one or a plurality of nucleophilic substances selected fromamong aromatic amino compounds, ammonia, aliphatic amino compounds,aromatic hydroxy compounds, aliphatic hydroxy compounds, water, aromaticmercapto compounds, and aliphatic mercapto compounds respectively toreact independently or sequentially or simultaneously with thequinizarin thereby inducing nucleophilic substitution of the halogenatom.

In the nucleophilic substances mentioned above, the primary aminecompounds are aniline compounds which are represented by the generalformula (5): ##STR6## wherein A independently stands for at least onemember selected from the class consisting of --COOR¹ (wherein R¹ standsfor a hydrogen atom or an alkyl group of 1 to 18, preferably 1 to 12,carbon atoms), sulfonic group, cyano group, alkyl groups of 1 to 8,preferably 1 to 6, carbon atoms, alkoxy groups of 1 to 8, preferably 1to 6 carbon atoms, and halogen atoms, and a is an integer in the rangeof 0 to 5, preferably 1 to 3. In this case, the aniline compound isdesired to have the 2 and 6 positions thereof both substituted. Asanother example of the primary amine compound, NHR² (wherein R² standsfor a hydrogen atom or an alkyl group of 1 to 18, preferably 1 to 12,carbon atoms) may be cited.

The reaction in this case is generally carried out in an organicsolvent. The organic solvents which are effectively usable for thisreaction include, for example, such inert solvents as nitrobenzene,acetonitrile, and benzonitrile, such nonprotonic polar solvents aspyridine, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, triethylamine, tri-n-butyl amine, dimethyl sulfone, and sulforan, such halogentype solvents as α-chloronephthalene, trichlorobenzene, dichlorobenzene,chloroform, and dichloroethane, and benzene, toluene, and xylene. It ispermissible to use the aforementioned nucleophilic substances like aminocompounds, hydroxy compounds and water by themselves or an aqueousammonia solution as a solvent in the reaction without using such anorganic solvent as mentioned above.

As a condensation agent, it is advantageous to use such an organic baseas triethyl amine or tri-n-butyl amine or an inorganic salt such aspotassium fluoride, potassium hydroxide, potassium carbonate, sodiumhydroxide, or sodium carbonate. When the nucleophilic substance itselfmanifests the nature as a condensation agent in such amino compounds asaniline, toluidine, anisidine, n-butyl amine, and n-octyl amine, the useof the condensation agent is not always found necessary. Alternatively,when the nucleophilic substance itself has a high reactivity, acondensation agent is not always necessary to use. The reactiontemperature is in the range of 20° to 200° C., though variable as withthe kind of reaction solvent. The substitution reaction of an aromaticamino compound is desired to be carried out at a temperature in therange of 50° to 180° C., that of ammonia or an aliphatic amino compoundin the range of 20° to 100° C., that of an aromatic hydroxy compound inthe range of 20° to 120° C., that of a hydroxy compound or an aliphatichydroxy compound in the range of 50° to 180° C., that of an aromaticmercapto compound in the range of 20° to 100° C., and that of analiphatic mercapto compound in the range of 50° to 180° C.

Incidentally, the quinizarin which has the 5, 6, 7, and 8 positions, orthe 5, 6 and 7 positions, or the 5, 6 and 8 positions, or the 5 and 6positions, or the 5 and 7 positions, or the 6 and 7 positions, or the 6position, or the 7 position thereof substituted with halogen atoms andis used as a starting material in the method under consideration can besynthesized, for example, by such a well-known reaction as aFriedel-Crafts reaction from phthalic anhydride or phthalic acid(preferably, phthalic anhydride) which has the 3, 4, 5 and 6 positions,or the 3, 4 and 5 positions, or the 3, 4 and 6 positions, or the 3 and 4positions, or the 4 and 5 positions, or the 3 and 5 positions, or the 4position, or the 5 position thereof substituted with hologen atoms, andhydroquinone or dimethoxy hydroquinones (preferably, dimethoxyhydroquinone), for example, using as an acylating agent anhydrousaluminum chloride, for example. When the halogens at the 5, 6, 7, and 8positions are fluorine atoms, the quinizarin can be synthesized by themethod introduced to the art by the present inventors (disclosed inJP-A-61-112,041 and described in Japanese Appplication No. 05-261,293).When the halogens are other than fluorine atoms, the synthesis can becarried out similar to that with fluorine atoms.

The other method of production comprises causing a phthalic anhydridederivative the phthalic anhydride structure of which has one to four ofthe 3, 4, 5 and 6 positions and at least either the 4 or 5 positionthereof formed of at least one member selected from the class consistingof secondary amino groups, alkylthio groups, and optionally substitutedphenylthio groups, and the remaining positions thereof formed of atleast one member selected from the class consisting of hydrogen atom,halogen atoms, amino group, hydroxy group, alkoxy groups, and optionallysubstituted phenoxy groups to react with hydroquinone or 1,4-dimethoxybenzene.

To be specific, this method produces the quinizarin compound by causinga phthalic anhydride derivative represented by the general formula (6):##STR7## wherein one to four of the W, X, Y, and Z positions and atleast either of X or Y position are formed of at least one memberselected from the class consisting of secondary amino groups, alkylthiogroups, and optionally substituted phenylthio groups and the remainingpositions are formed of at least one member selected from the classconsisting of hydrogen atom, halogen atoms, amino group, hydroxy group,alkoxy groups, and optionally substituted phenoxy groups to react withhydroquinone or 1,4-dimethoxy benzene.

The derivative of phthalic anhydride or phthalic acid having the benzenering of phthalic anhydride partly or wholly substituted by a compoundselected from among halogen atoms, aromatic amino compounds, ammonia,aliphatic amino compounds, aromatic hydroxy compounds, aliphatic hydroxycompounds, water, aromatic mercapto compounds, and aliphatic mercaptocompounds is produced by causing one or a plurality of nucleophilicsubstances selected from among aromatic amino compounds, aliphatic aminocompounds, aromatic hydroxy compounds, aliphatic hydroxy compounds,aromatic mercapto compounds, and aliphatic mercapto compoundsrespectively to react independently or sequentially or simultaneouslywith a halogenated phthalic anhydride or a halogenated phthalic acidsuch as, for example, tetrachlorophthalic anhydride, tetrafluorophthalicanhydride, and tetrafluorophthalic acid thereby inducing nucleophilicsubstitution of the halogen atom.

The reaction temperature is in the range of 20° to 200° C., thoughvariable as with the kind of reaction solvent. The substitution reactionof an aromatic amino compound is desired to be carried out at atemperature in the range of 50° to 180° C., that of ammonia or analiphatic amino compound in the range of 20° to 100° C., that of anaromatic hydroxy compound in the range of 20° to 120° C., that of ahydroxy compound or an aliphatic hydroxy compound in the range of 50° to180° C., that of an aromatic mercapto compound in the range of 20° to100° C., and that of an aliphatic mercapto compound in the range of 50°to 180° C. The reaction in this case is generally carried out in anorganic solvent. The organic solvents which are effectively usable forthis reaction include, for example, such inert solvents as nitrobenzene,acetonitrile, and benzonitrile, such nonprotonic polar solvents aspyridine, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, triethylamine, tri-n-butyl amine, dimethyl sulfone, and sulforan, such halogentype solvents as α-chloronephthalene, trichlorobenzene, dichlorobenzene,chloroform, and dichloroethane, and benzene, toluene, and xylene. It ispermissible to use the aforementioned nucleophilic substances like aminocompounds, hydroxy compounds or water by themselves or an ammoniasolution as a solvent in the reaction without using such an organicsolvent as mentioned above.

As a condensation agent, it is advantageous to use such an organic baseas triethyl amine or tri-n-butyl amine or an inorganic base such aspotassium fluoride, potassium hydroxide, potassium carbonate, sodiumhydroxide, or sodium carbonate. When the nucleophilic substance itselfmanifests the nature as a condensation agent in such amino compounds asaniline, toluidine, anisidine, n-butyl amine, and n-octyl amine, the useof the condensation agent is not always found necessary. Thecondensation agent is not always found necessary when the nucleophilicsubstance itself possesses strong reactivity.

The derivative of phthalic anhydride or phthalic acid having the benzenering of phthalic anhydride substituted partly or wholly by a compoundselected from among halogen atoms, aromatic amino compounds, ammonia,aliphatic amino compounds, aromatic hydroxy compounds, aliphatic hydroxycompounds, water, aromatic mercapto compounds, and aliphatic mercaptocompounds can be obtained by hydrolyzing in accordance with thegenerally adopted method the phthalonitrile having the benzene ring ofphthalonitrile partly or wholly substituted preparatorily by a halogenatom, an aromatic amino compound, ammonia, an aliphatic amino compound,an aromatic hydroxy compound, an aliphatic hydroxy compound, water, anaromatic mercapto compound, or an aliphatic mercapto compound inaccordance with the method taught by Ishikawa et al., in the Journal ofOrganic Synthesis Society, Vol. 21, No. 8, page 792 (1971) or the methoddisclosed by the present inventors in Japanese Patent Applicatoin No.04-28,185, for example.

When the quinizarin compound mentioned above has one secondary aminogroup, it is useful as a magenta dye. When this quinizarin compound hastwo secondary amino groups, it is useful as a cyan dye.

This invention is further directed to an electrophotographic grade colortoner composition which comprises at least one coloring agent selectedfrom the group consisting of the magenta dye and the cyan dye and abinder resin.

As the binder resin in the color toner of this invention, any of thebinder resins heretofore known to the art may be used. Concrete examplesof the well-known binder resins include styrene and derivatives thereofsuch as polystyrene, polyvinyl toluene, poly-α-methylstyrene,poly-p-chlorostyrene, and aminostyrene, styrene type copolymers such asstyrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer,styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer,styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer,styrene-ethyl methacrylate copolymer, styrene-butyl methacrylatecopolymer, styrene-α-chloromethyl methacrylate copolymer,styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer,styrene-butadiene copolymer, styrene-isoprene copolymer,styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer,and styrene-maleic ester copolymers, homopolymers and copolymers ofmethacrylic acid and methacrylate esters such as methyl methacrylate,ethyl methacrylate, and butyl methacrylate, homopolymers and copolymersof acrylic acid and acrylic esters such as methyl acrylate, ethylacrylate, butyl acrylate, and 2-ethylhexyl acrylate, dienes such asbutadiene and isoprene, homopolymers of vinyl monomers such asacrylonitrile, vinyl ethers, maleic acid and maleic esters, maleicanhydride, vinyl chloride, and vinyl acetate and copolymers of the vinyltype monomers mentioned above with other monomers, homopolymers andcopolymers of olefin type compounds such as ethylene and propylene,polyesters, polyamides, polyurethanes, rosin, modified rosins, terpeneresins, phenol resins, aliphatic and alicyclic hydrocarbon resins,aromatic petroleum resins, chlorinated paraffins, and paraffin waxes.These binder resins can be used either singly or in the form of amixture of two or more members.

The electrification constitutes one of the important qualities of atoner. The control of this electrification of the toner may be effectedwith the resin or the coloring agent by itself. Otherwise, it may beattained by the addition of such an antistatic agent as is incapable ofaffecting the color tone. Any of the well-known antistatic agents can beadopted for use in the color toner of this invention. Concrete examplesof the well-known antistatic agents which are usable herein includemetal complexes of salicylic acid, organic salts of boron, quaternaryammonium salts, aluminum compounds, silicone derivatives, zinccompounds, metal complexes of imidazole, and pyridinium salts.

The amount of the antistatic agent to be added properly is in the rangeof 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight,based on the amount of the binder resin. The use of the antistatic agentherein may be attained by having the agent added to and mixed with thebinder resin. It may be otherwise accomplished by having the agentdeposited on the surface of toner particles by a varying methodavailable for the deposition.

Besides, the color toner of this invention may incorporate therein asolid electrolyte, a macromolecular electrolyte, a charge transfercomplex, a conductor such as tin oxide or other similar metal oxide, asemiconductor, a ferroelectric substance, or a magnetic substance forthe purpose of controlling the electric characteristics of the toner. Itmay also incorporate therein such additives as varying plasticizers andmold release agents for the purpose of controlling various physicalproperties such as thermal properties. Further, it may incorporatetherein such minute inorganic particles as fine powders of TiO₂, Al₂ O₃,and SiO₂ and colloidal silica or such minute organic particles as fineresin powders for the purpose of imparting improved flowability andenhanced resistance to coagulation to the toner.

For the production of the color toner of this invention, any of themethods generally adopted heretofore and various other methods may beadopted. For example, the common method which produces a color toner byuniformly mixing a resin, a coloring agent, and optionally variousadditives by the use of a varying mixer such as a ball mill, thenmelting and kneading the resultant mixture by the use of a pressurekneader, an extruder, or a roll mill, subsequently coarsely pulverizingthe produced blend as with a hammer mill, further finely pulverizing thecoarse lumps as with an air jet type fine pulverizer, and classifyingthe resultant powder and separating a fine powder may be adopted.Otherwise, the method which produces a color toner by polymerizing apolymeric monomer by such an operation as emulsion polymerization,suspension polymerization, dispersion polymerization, or seedpolymerization in the presence of a coloring agent thereby forming afine powder of colored resin having a prescribed average particlediameter may be adopted. Alternatively, the method which produces acolor toner by preparatorily synthesizing a fine powder of resin havinga prescribed average particle diameter by the same technique ofpulverization and classification as adopted in the ordinary productionof a toner or polymerizing a polymeric monomer by such an operation asemulsion polymerization, suspension polymerization, dispersionpolymerization, or seed polymerization and coloring or dyeing the powderwith a coloring agent may be adopted.

The ratio of the amount of the binder resin to that of the dye mentionedabove is in the range of 0.1 to 10 parts by weight, preferably 1 to 6parts by weight, of the dye to 100 parts by weight of the binder resin.

The color toner of this invention can be mixed with a carrier to giverise to an electrophotographic developer. The carriers which can beeffectively used in this case include, for example, such well-knowncarriers as iron powder, nickel powder, glass beads, and ferrite powderand further include, for example, those which are obtained by coatingthe surface of such well-known carriers with styrene-acrylic estercopolymers, styrene-methacrylate ester copolymers, acrylic esterpolymers, methacrylate ester polymers, silicone resins, polyamideresins, ionomer resins, polyphenylene, sulfide resins, or mixturesthereof.

This invention is further directed to a thermal-transfer recording sheetwhich is provided on a substrate with a coloring material layercontaining at least one dye selected from the group consisting of themagenta dye and the cyan dye both mentioned above.

The transfer sheet using the dye of this invention is produced bypreparing a thermal-transfer recording ink composed of a dye, a binderresin, and a solvent, applying the ink on a transfer sheet substrate,and drying the wet applied layer of the ink. The concentration of thedye in the ink is generally in the range of 1 to 5% by weight.

The binder resin to be used for the preparation of the ink may be any ofthe binder resins heretofore well known in the art. Concrete examples ofthe binder resins which are advantageously used herein include suchcellulose type resins as ethyl cellulose, hydroxyethyl cellulose, ethylhydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, andcellulose acetate and such vinyl type resins as polyvinyl butyral,polyvinyl acetoacetal, polyvinyl pyrrolidone, and polyacrylamide. Amongother binder resins cited above, polyvinyl butyral proves to beparticularly desirable from the standpoints of resistance to heat andease of transfer of dye.

The media which are advantageously usable for the preparation of the inkinclude, for example, such aromatic compounds as toluene, xylene, andchlorobenzene, such esters as ethyl acetate and butyl acetate, suchketones as acetone, methylethyl ketone, methyl isobutyl ketone, andcyclohexanone, such alcohols as methanol, ethanol, propanol, andbutanol, such cellosolves as methyl cellosolve and ethyl cellosolve, andsuch hydrocarbons as ligroine, cyclohexane, and kerosene.

As the base material for the transfer sheet to which the ink is applied,any of the heretofore well-known materials which excel in resistance toheat and strength may be used. Concrete examples of the base materialsadvantageously used herein include polyester film, polystyrene film,polypropylene film, polysulfone film, polycarbonate film, Alamides film,polyvinyl alcohol film, and cellophane. Among other base materials citedabove, polyester film proves to be particularly desirable. The thicknessof the base material properly used herein is in the range of 2 to 20 μm,preferably 3 to 10 μm.

The application of the ink to the base material of the transfer sheetcan be effected by the use of a bar coater, a roll coater, a gravurecoater, or a knife coater. The thickness of the applied layer of the inkafter drying is desired to be in range of 0.1 to 5 μm, preferably 0.4 to2.0 μm.

The recording materials on which the transfer sheet is used effectivelyinclude, for example, polyolefin type resins such as polyethylene andpolypropylene; halogen type polymers such as polyvinyl chloride andpolyvinylidene chloride; vinyl type polymers such as polyvinyl alcohol,polyvinyl acetate, and polyacrylic acid; polyester type resins such aspolyethylene terepthalate and polybutylene terephthalate; polystyreneresin, polyamide resin, resins of the copolymers of such olefins asethylene and propylene with other vinyl polymers; cellulose type resinssuch as ionomer and cellulose diacetate; and fibers, woven fabrics,films, sheets, and formed articles made of polycarbonate, polysulfone,and polyimide.

Among other recording materials cited above, fibers, woven fabrics,films, sheets, and processed papers made of polypropylene orpolyethylene terephthalate prove to be particularly desirable.

Further, this invention is directed to an optical recording medium whichcontains the aforementioned quinizarin compound in the recording layerformed on the substrate.

This invention is also directed to a tracing type optical recordingmedium adapted for a compact disk and composed of a transparent resinoussubstrate, a recording layer formed on the substrate, and a metallicreflecting layer, which optical recording medium has the aforementionedquinizarin compound contained in the recording layer mentioned above.

The substrate of the disk to be used in this case is desired to bepervious to the light which is used for recording a signal or readingthe recorded signal. The transmittance of this substrate relative tolight is desired to be not less than 85% and the optical anisotropy isdesired to be as small as possible. Concrete examples of the disksubstrates desirably used herein include substrates which are made ofglass, acrylic resin, polycarbonate resin, polyester resin, polyamideresin, vinyl chloride resin, polystyrene resin, and epoxy resin. Amongother substrates cited above, those made of polycarbonate resin prove tobe particularly desirable from the standpoints of opticalcharacteristics, ease of forming, and mechanical strength.

The dye mentioned above is first deposited in the form of a layer on thesubstrate and the metallic reflecting film layer is formed thereon. Themetals which are usable for the reflecting layer include, for example,Al, Ag, Au, Cu, and Pt, for example. This reflecting layer is generallyformed by vacuum deposition or spattering.

For the formation of the recording layer containing the dye on thesubstrate in the optical recording medium of this invention, it isgenerally desirable to use the method of coating. This coating isaccomplished by such an operation as spin coating, dip coating, or rollcoating. Among other coating operations mentioned above, the spincoating operation proves to be particularly desirable. The organicsolvent to be used in the coating operation ought to avoid corroding thesubstrate. Concrete examples of the organic solvents which are usableadvantageously herein include aliphatic and alicyclic hydrocarbons suchas hexane, octane, and cyclohexane and alcohol type solvents such asmethyl alcohol, isopropyl alcohol, allyl alcohol, methyl cellosolve, andethyl cellosolve. Since the aforementioned dyes of this inventionexhibit particularly high solubility in alcohol type solvents, it isdesirable to use these solvents in the coating operation underconsideration.

The CD of this invention, in view of the interchangeability of players,is required to exhibit a reflectance of not less than 60% relative tothe laser beam passed through the substrate and used for reading. Theadjustment of the reflectance is attained by optimizing the filmthicknesses of the relevant dyes being used in the CD. Generally, thesefilm thicknesses are desired to be in the range of 50 nm to 300 nm.

Further, this invention is directed to an ink jet grade ink compositionwhich comprises at least one dye selected from the group consisting ofthe magenta dye and the cyan dye both mentioned above and a vehicle.

The ink jet recording is known in various types such as continuousinjection type, intermittent injection type, on-demand type, and inkmist type, depending on the kind of system. The ink jet grade ink isalso known in numerous types such as water type, water-solvent type,solvent type, and solid type. The ink of the water type is generallypredominant. Particularly, the ink of the solid type is normally in asolid or semi-solid state at a normal temperature. The recording withthis ink is attained by a procedure which comprises heating this solidink with an ink jet device, spouting the liquefied ink through the inkjet device, causing the hot ink liquid to land on a given surface, andallowing the deposited dots of ink liquid to cool and solidify. The inkof the solid type can produce prints on various materials ranging fromthe OHP film to the tissue paper and is characterized by producingprints of ideal contrast. Though the solid ink has the prospect ofbright future, none of the pigments or dyes heretofore available for thesolid ink satisfies the two aspects of lightfastness and color tonesimultaneously.

The dye of this invention exhibits high solubility in solvents, enjoysvery high lightfastness, and excels in color tone. Thus, it manifests anoutstanding effect in any of the types of ink mentioned above. Amongother types cited above, this dye proves to be suitable for the solventtype ink and the solid or semi-solid type ink, especially for the solidor semi-solid type ink.

The dye of this invention can be used as a coloring agent for the ink ofthe new system which, as disclosed in Fine Chemical, 1991, Vol. 20, No.21, page 15, utilizes the electroviscous effect of ink as in theoperation of effecting the ink jet recording by dispersing polymerparticles in an insulating medium, causing change of the viscosity ofthe resultant dispersion by the application of an electric field, andcontrolling the discharge of the ink.

The vehicles which are effectively usable for the dry oil type ink inthis invention include, for example, a rosin-modified phenol resin, apetroleum type resin, or an alkyd resin as the resin component, andlinseed oil, tung oil, or synthetic dry oil as the dry oil component,and a petroleum type solvent as the solvent component. The vehicleseffectively usable for the organic solvent type ink include, forexample, a polyamide resin, a vinyl type nitrocellulose resin, or anacryl type resin as the resin component and toluene, an ester typesolvent, a ketone type solvent, or an alcohol type solvent as thesolvent component. The vehicles effectively usable for the water type orwater-solvent type ink include a maleic acid type resin or an acrylictype resin as the resin component and water, an alcohol type solvent, ora glycol type solvent for the solvent component. The vehicleseffectively usable for the solid or semi-solid type ink include thecomposition obtained by combining a fatty acid such as oleic acid with awax as an additive, the composition obtained by combining a fatty acidsuch as oleic acid as a vehicle containing benzyl ether with a wax as anadditive, or the composition having a wax as a main component.

The wax to be used as a vehicle component in the solid or semi-solidtype ink may be any of the waxes heretofore well known in the art.Concrete examples of the well-known waxes include sumac wax, candelillawax, carnauba wax, microcrystalline wax, paraffin wax, Fischer-Tropschwax, polyolefin wax, various low molecular weight polyethylenes,beeswax, spermaceti wax, ibotallow, wool wax, ceramic wax, candelillawax, petrolactam, fatty acid ester waxes, fatty acid amide waxes,polymers of long-chain acrylate or long-chain methacrylate such aslong-chain acrylates (such as, for example, stearyl acrylate and behenylacrylate) or long-chain methacrylates (such as, for example, stearylmethacrylate and behenyl methacrylate), acryl or methacryl copolymerscontaining such long-chain acrylates or long-chain methacrylates asmentioned above, and waxes obtained from acryl or methacryl copolymerswith monomers having other vinyl groups. These waxes can be used eithersingly or in the form of a mixture of two or more members. Further, theymay be combined in a suitable ratio as by graft polymerization.

The amount of the wax to be used is in the range of 0.5 to 99.0% byweight, based on the amount of the ink composition. The amount of thedye to be used is in the range of 0.5 to 10% by weight, preferably 1.0to 5.0% by weight, based on the amount of the ink composition.

This invention is further directed to a color filter which contains atleast one dye selected from the class consisting of quinizarin compoundsaccording to this invention in a filter substrate.

The following methods are available for the production of the colorfilter of this invention.

(1) The method which produces a color filter by causing the dye of thisinvention, either alone or in combination with other dye, to be mixedwith 1 to 100 parts by weight per part by weight of the dye of athermoplastic resin such as polystyrene, polymethyl methacrylate,polycarbonate, polyester, or polyvinyl chloride and forming theresultant mixture by such an operation as injection molding orelongation.

(2) The method which comprises causing the dye of this invention, eitheralone or in combination with other dye, to be solved together with 1 to100 parts by weight per part by weight of the dye of such a binder aspolystyrene, polymethyl methacrylate, or polycarbonate in a solvent, andforming a film of the resultant solution as by casting or spin coatingor forming a substrate of the solution as by vacuum deposition.

(3) The method which comprises causing the dye of this invention, eitheralone or in combination with other dye, to be preparatorily solved in 1to 100 parts by weight per part by weight of the dye of a lightsensitive resin, forming a film of the resultant solution as by castingor spin coating on a substrate, and patterning the formed film as byirradiation of light.

In the method of (3) mentioned above, the patterning of the dye layercan be carried out on an optically transparent substrate. The substratethus used has no particular restriction except for the requirement thatit should allow the dye layer to be patterned as required and ensureproduction of a color filter possessed of a prescribed function.Concrete examples of the substrates effectively usable herein includeglass sheet and films or sheets of such resins as polyvinyl alcohol,hydroxyethyl cellulose, methyl methacrylate, polyester, butyral,polyamide, polyethylene, vinyl chloride, vinylidene chloride,polycarbonate, polyolefin copolymer resins, vinyl chloride copolymerresins, vinylidene chloride copolymer resins, and styrene copolymerresins. The patterned dye layer may be integrally formed with what isintended to be utilized as a color filter.

In the method for the production of the color filter of this invention,the light sensitive resist grade resin to be used in combination withthe dye of this invention as described above is only required to becapable of being solidified with light or to be a photo-setting resin.It may be any of the resins containing light sensitive groups which havewon wide recognition through introduction in various pieces ofliterature ("Recording Materials and Light Sensitive Resins," compiledby the Japan Society for the Promotion of Science and published byGakkai Shuppan Center and "Photopolymer Handbook," compiled byPhotopolymer Meeting and published by Kogyo Chosakai).

Concrete examples of the light sensitive resist grade resins include asfollowing:

(a) Water-soluble photosensitive resins having a photosensitive group,such as a polyvinyl alcohol resin having a stilbazolium group,

(b) Oil-soluble photosensitive resins having a photosensitive group,such as a cinnamate type photo-crosslinkable photosensitive resin, abisazide type photo-decomposing cross-linkable photosensitive resin, andan o-quinoneazide type decomposing polar modified photosensitive resin,

(c) Resin composition containing a photo-crosslinkable resin and aphoto-crosslinking agent:

(c1) Photo-crosslinkable resins including such animal protein resins asgelatin, casein and glue, such cellulose type resins ascarboxymethylcellulose and hydroxyethyl cellulose, vinyl polymerizationtype resins of polyvinyl alcohol, polyvinyl pyrrolidone, polyvinylmethylether, polyacrylic acid and polyacrylamide and copolymers thereof,such ring opening polymerization type resins as polyethylene glycol andpolyethylene imine, condensation resins such as water-soluble nylon,such oil-soluble resins as butyral resin, styrene-maleic acidcopolymers, chlorinated polyethylene, chlorinated polypropylene,polyvinyl chloride, vinyl chloride, vinyl acetate copolymers, polyvinylacetate, acrylic resin, polyester, phenolic resin and polyurethane,

(c2) Examples of the photo-crosslinking agent;

dichromates, chromates, diazo compounds, and bisazide compounds,

(d) Resin composition comprising a photo-crosslinkable resin, apolymerizable monomer and an initiator,

(d1) Polymerizable monomers such as (meth)acrylic acid, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl acetate, N-vinylpyrrolidone, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide,polyethylene glycol di(meth)acrylate, methylenebis(meth)acrylamide,styrene, and (meth)acrylonitrile,

(d2) Initiators including photo-decomposition type initiators such asazobisisobutyronitrile and benzoisoalkylether, hydrogen transfer typeinitiators such as benzophenone, anthraquinone and 2-phenylacridine, andelectron transfer type condensation initiators such asbenzanthrone/triethanolamine, methylene blue/benzenesulfinic acid saltand carbon tetrachloride/manganese carbonyl.

Among other resist resins known to the art, those resist resins whichcontain acrylic resins and epoxy type resins prove to be particularlydesirable.

Now, this invention will be described more specifically below withreference to working examples.

The physicochemical properties of the compounds produced in the workingexamples are shown in the following tables. In these tables, thesolubility is rated on the three-point scale, wherein Δ stands for asolubility of less than 1% by weight, ∘ for a solubility in theapproximate range of 1 to 3% by weight, and ⊚ for a solubility of notless than 3% by weight.

EXAMPLES 1 AND 2

In a four-neck flask of 500 cc in inner volume, 400 cc of acetonitrile,3 g (9.61 mmols) of 5,6,7,8-tetrafluoroquinizarin, about 1.8 g (19.3mmols) of aniline, and 1.34 g (23.1 mmols) of potassium fluoride wereplaced and refluxed for reaction for about 24 hours. After the reaction,the reaction solution was filtered to separate potassium fluoride,distilled to expel acetonitrile, then poured into an aqueoushydrochloric acid solution to allow separation by filtration of solidsformed by the reaction. The solids were washed with water and dried toobtain 4.3 g of a crude product. This crude product was refined by meansof a column packed with silica gel (Wakogel C-200) to obtain 1.23 g of6-anilino-5,7,8-trifluoroquinizarin dye (1)! (yield 33.2 mol %) and 0.41g of 6,7-dianilino-5,8-difluoroquinizarin dye (120)! (yield 9.3 mol %).The physical properties of the dye (1) and the analyses used for theidentification of this compound are shown in Table 1 and the physicalproperties of the dye (120) and the analyses used for the identificationof this compound in Table 3.

EXAMPLES 3 AND 4

By following the procedures of Examples 1 and 2 while using about 3.7 g(19.1 mmols) of o-aminobenzoic acid-n-butyl in place of aniline, 1.47 gof 6-(o-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin dye (5)! (yield31.5 mol %) and 0.65 g of6,7-bis(o-butoxycarbonylanilino)-5,8-difluoroquinizarin dye (122)!(yield 10.3 mol %) were obtained. The physical properties of the dye (5)and the analyses used for the identification of this compound are shownin Table 1 and the physical properties of the dye (122) and the analysesused for the identification of this compound in Table 3.

EXAMPLES 5 AND 6

By following the procedures of Examples 1 and 2 while using about 3.2 g(19.4 mmols) of m-aminoethyl benzoate in place of aniline, 1.42 g of6-(m-ethoxycarbonylanilino)-5,7,8-trifluoroquinizarin dye (4)! (yield32.3 mol %) and 0.56 g of6,7-bis(m-ethoxycarbonylanilino)-5,8-difluoroquinizarin dye (121)!(yield 9.7 mol %) were obtained. The physical properties of the dye (4)and the analyses used for the identification of this compound are shownin Table 1 and the physical properties of the dye (121) and the analysesused for the identification of this compound in Table 3.

EXAMPLE 7

By following the procedures of Examples 1 and 2 while using about 4.8 g(19.3 mmols) of m-aminobenzoic acid-n-octyl in place of aniline, 1.48 gof 6-(m-octyloxycarbonylanilino)-5,7,8-trifluoroquinizarin dye (8)!(yield 28.4 mol %) was obtained. The physical properties of this dye andthe analyses used for the identification of this compound are shown inTable 1.

EXAMPLE 8

By following the procedures of Examples 1 and 2 while using about 3.7 g(19.1 mmols) of p-aminobenzoic acid-n-butyl in place of aniline, 1.53 gof 6-(p-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin dye (6)! (yield32.8 mol %) was obtained. The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table1.

EXAMPLES 9 AND 10

By following the procedures of Examples 1 and 2 while using about 2.4 g(19.5 mmols) of o-anisidine in place of aniline, 1.34 g of6-(o-methoxyanilino)-5,7,8-trifluoroquinizarin dye (14)! (yield 33.6mol%) and 0.40 g of 6,7-bis(o-methoxyanilino)-5,8-difluoroquinizarin dye(131)! (yield 8.0 mol%) were obtained. The physical properties of thedye (14) and the analyses used for the identification of this compoundare shown in Table 2 and the physical properties of the dye (131) andthe analyses used for the identification of this compound in Table 4.

EXAMPLES 11 AND 12

By following the procedures of Examples 1 and 2 while using about 2.4 g(19.5 mmols) of m-anisidine in place of aniline, 1.21 g of6-(m-methoxyanilino)-5,7,8-trifluoroquinizarin dye (16)! (yield 30.3mol%) and 0.54 g of 6,7-bis(m-methoxyanilino)-5,8-difluoroquinizarin dye(133)! (yield 10.8 mol%) were obtained. The physical properties of thedye (16) and the analyses used for the identification of this compoundare shown in Table 3 and the physical properties of the dye (133) andthe analyses used for the identification of this compound in Table 4.

EXAMPLE 13 AND 14

By following the procedures of Examples 1 and 2 while using about 2.4 g(19.5 mmols) of p-anisidine in place of aniline, 1.39 g of6-(p-methoxyanilino)-5,7,8-trifluoroquinizarin dye (15)! (yield 34.8mol%) and 0.56 g of 6,7-bis(p-methoxyanilino)-5,8-difluoroquinizarin dye(132)! (yield 11.2 mol%) were obtained. The physical properties of thedye (15) and the analyses used for the identification of this compoundare shown in Table 3 and the physical properties of the dye (132) andthe analyses used for the identification of this compound in Table 4.

EXAMPLES 15 AND 16

By following the procedures of Examples 1 and 2 while using about 2.9 g(19.4 mmols) of 4-tert.-butyl aniline in place of aniline, 1.26 g of6-(p-tertiary butylanilino)-5,7,8-trifluoroquinizarin dye (13)! (yield29.7 mol %) and 0.43 g of 6,7-bis(p-tertiarybutylanilino)-5,8-difluoroquinizarin dye (130)! (yield 7.8 mol %) wereobtained. The physical properties of the dye (13) and the analyses usedfor the identification of this compound are shown in Table 23 and thephysical properties of the dye (130) and the analyses used for theidentification of this compound in Table 4.

EXAMPLE 17

In a four-neck flask of 500 cc in inner volume, 400 cc of chloroform, 3g (9.61 mmols) of 5,6,7,8-tetrafluoroquinizarin, about 0.7 g (9.57mmols) of n-butyl amine and 0.67 g (11.5 mmols) of potassium fluoridewere placed and left reacting at room temperature for about 24 hours.After the reaction, the reaction solution was filtered to separatepotassium fluoride, distilled to expel chloroform, and then washed withwater and dried to obtain 3.1 g of a crude product. This crude productwas refined by means of a column packed with silica gel (Wakogel C-200)to obtain 2.92 g of 6-butylamino-5,7,8-trifluoroquinizarin dye (117)!(yield 83.2 mol%). The physical properties of the dye and the analysesused for the identification of this compound are shown in Table 2.

EXAMPLE 18

By following the procedure of Example 17 while increasing the amount ofn-butyl aniline to about 2.1 g (28.7 mmols) and that of potassiumfluoride to 2.01 g (34.0 mmols), 2.27 g of5,6,7-tris(butylamino)-8-fluoroquinizarin dye (248)! (yield 50.1 mol%)was obtained. The physical properties of this dye and the analyses usedfor the identification of this compound are shown in Table 5.

EXAMPLE 19

In a four-neck flask of 500 cc in inner volume, 400 cc of acetonitrile,3 g (9.61 mmols) of 5,6,7,8-tetrafluoroquinizarin, about 0.95 g (9.58mmols) of cyclohexyl amine, and 0.67 g (11.5 mmols) of potassiumfluoride were placed and left reacting at 50° C. for about 24 hours.After the reaction, the reaction solution was filtered to separatepotassium fluoride, distilled to expel acetonitrile, and then washedwith water and dried to obtain 3.3 g of a crude product. This crudeproduct was refined by means of a column packed with silica gel (WakogelC-200) to obtain 2.02 g of 6-cyclohexylamino-5,6,8-trifluoroquinizarindye (119)! (yield 53.7 mol %). The physical properties of the dye andthe analyses used for the identification of this compound are shown inTable 2.

EXAMPLES 20 AND 21

In a four-neck flask of 200 cc in inner volume, 100 g ofp-aminobenzonitrile and 3 g (9.61 mmols) of5,6,7,8-tetrafluoroquinizarin were placed and left reacting at 120° C.for about 4 hours. After the reaction, the reaction solution was thrownin a mixture of about 400 cc of acetone with about 500 cc of water andacidified with concentrated hydrochloric acid to induce separation ofsolids. The solids were separated by filtration, washed with water, anddried to obtain 4.8 g of a crude product. Then, this crude product wasrefined by means of a column packed with silica gel (Wakogel C-200) toobtain 1.21 g of 6-(p-cyanoanilino)-5,7,8-trifluoroquinizarin dye (10)!(yield 30.7 mol %) and 0.45 g of6,7-bis(p-cyanoanilino)-5,8-difluoroquinizarin dye (126)! (yield 9.2 mol%) were obtained. The physical properties of the dye (10) and theanalysis used for the identification of this compound are shown in Table1 and the physical properties of the dye (126) and the analyses used forthe identification of this compound in Table 4.

EXAMPLE 22

Four (4) g (12.6 mmols) of 4-cyanoanilino-3,5-6-trifluorophthalicanhydride and 4.34 g (31.4 mmols) of p-dimethoxy benzene were addedpiecemeal into a fused mass (130° to 135° C.) consisting of 50 g (0.37mol) of anhydrous aluminum chloride and 5 g of sodium chloride. Theresultant mixture was then heated and kept stirred at 180° C. for onehour. Then, the reaction solution was poured into ice water and then 50cc of concentrated hydrochloric acid was added thereto to induceseparation of solids. The solids were separated by filtration, washedwith water, and dried to obtain 3.2 g of a crude product. Then, thecrude product was refined by means of a column packed with silica gel(Wakogel C-200) to obtain 1.92 g of6-(p-cyanoanilino)-5,7,8-trifluoroquinizarin dye (10)! (yield 37.2 mol%).

Mass spectrum:

m/e=410 (M⁺, 100)

m/e=391 (M⁺ -19, 20)

    ______________________________________                                        Elementary analyses:                                                                     C (%) H (%)     N (%)   F (%)                                      ______________________________________                                        Theoretical value                                                                          61.47   2.21      6.83  13.89                                    Measured value                                                                             61.52   2.23      6.79  13.82                                    ______________________________________                                    

EXAMPLE 23

By following the procedures of Examples 20 and 21 while using 100 g ofp-nitroaniline in place of p-aminobenzonitrile and changing the reactiontemperature to 160° C., 1.17 g of6-(p-nitroanilino)-5,7,8-trifluoroquinizarin dye (12)! (yield 28.3 mol%) was obtained. The physical properties of this dye and the analysesused for the identification of this compound are shown in Table 2.

EXAMPLES 24 AND 25

By following the procedures of Examples 20 and 21 while using 100 g of2,6-diethyl aniline in place of p-aminobenzonitrile, 1.36 g of6-(2,6-diethylanilino)-5,7,8-trifluoroquinizarin dye (18)! (yield 32.1mol %) and 0.58 g of 6,7-bis(2,6-diethylanilino)-5,8-difluoroquinizarindye (137)! (yield 10.6 mol %) were obtained. The physical properties ofthe dye (18) and the analyses used for the identification of thiscompound are shown in Table 3 and the physical properties of the dye(137) and the analyses used for the identification of this compound inTable 5.

EXAMPLE 26

In a four-neck flask of 500 cc in inner volume, 400 c of acetonitrile, 3g (8.21 mmols) of 6-butylamino-5,7,8-trifluoroquinizarin dye (117)!,about 0.92 g (9.88 mmols) of aniline, and 0.57 g (9.81 mmols) ofpotassium fluoride were placed and refluxed for reaction for about 24hours. After the reaction, the reaction solution was filtered toseparate potassium fluoride, distilled to expel acetonitrile, and thenwashed with water and dried to obtain 3.9 g of a crude product. Then,this crude product was refined by means of a column packed with silicagel (Wakogel C-200) to obtain 1.20 g of6-anilino-7-butylamino-5,8-difluoroquinizarin dye (229)! (yield 33.3 mol%). The physical properties of this dye and the analyses used for theidentification of this compound are shown in Table 5.

EXAMPLE 27

By following the procedure of Example 26 while using 1.63 g (9.87 mmols)of m-aminoethyl benzoate in place of aniline, 1.27 g of6-(m-ethoxycarbonylanilino)-7-butylamino-5,8-difluoroquinizarin dye(227)! (yield 30.3 mol %) was obtained. The physical properties of thisdye and the analyses used for the identification of this compound areshown in Table 4.

EXAMPLE 28

By following the procedure of Example 26 while using 1.21 g (9.82 mmols)p-anisidine in place of aniline, 1.31 g of6-(p-methoxyanilino)-7-butylamino-5,8-difluoroquinizarin dye (228)!(yield 34.1 mol %) was obtained. The physical properties of this dye andthe analyses used for the identification of this compound are shown inTable 5.

EXAMPLE 29

In a four-neck flask of 500 cc in inner volume, 400 cc of acetonitrile,3 g (9.61 mmols) of 5,6,7,8-tetrafluoroquinizarin, 2.12 g (19.2 mmols)of thiophenol, and 1.34 g (23.1 mmols) of potassium fluoride were placedand refluxed for reaction for about 8 hours. After the reaction, thereaction solution was filtered to separate potassium fluoride, distilledto expel acetonitrile, and then dried to obtain 4.6 g of6,7-diphenylthio-5,8-difluoroquinizarin dye (298)! (yield 97.2 mol %).The physical properties of this dye and the analyses used for theidentification of this compound are shown in Table 6.

EXAMPLE 30

By following the procedure of Example 29 while using 4.35 g (19.2 mmols)of 4-mercapto-2,3,5-6-tetrafluorobenzoic acid in place of thiophenol,5.45 g of6,7-bis(4-carboxy-2,3,5,6-tetrafluorophenylthio)-5,8-difluoroquinizarindye (299)! (yield 78.3 mol %) was obtained. The physical properties ofthis dye and the analyses used for the identification of this compoundare shown in Table 7.

EXAMPLE 31

By following the procedure of Example 29 while using 3.98 g (19.2 mmols)of 4-mercapto-2,3,5-6-tetrafluorobenzonitrile in place of thiophenol,4.83 g of6,7-bis(4-cyano-2,3,5,6-tetrafluorophenylthio)-5,8-difluoroquinizarindye (300)! (yield 73.2 mol %) was obtained. The physical properties ofthis dye and the analyses used for the identification of this compoundare shown in Table 7.

EXAMPLE 32

By following the procedure of Example 29 while using 2.43 g (19.3 mmols)of p-mercaptophenol in place of thiophenol, 4.41 g of6,7-bis(p-hydroxyphenylthio)-5,8-difluoroquinizarin dye (301)! (yield87.5 mol %) was obtained. The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table7.

EXAMPLE 33

By following the procedure of Example 29 while using 2.69 g (19.2 mmols)of p-methoxybenzenethiol in place of thiophenol, 4.52 g of6,7-bis(p-methoxyphenylthio)-5,8-difluoro-quinizarin dye (302)! (yield85.1 mol %) was obtained. The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table7.

EXAMPLE 34

By following the procedure of Example 29 while using 2.28 g (19.2 mmols)of hexanethiol in place of thiophenol, 4.51 g of6,7-dihexylthio-5,8-difluoroquinizarin dye (303)! (yield 92.3 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 6.

EXAMPLE 35

By following the procedure of Example 29 while using 2.81 g (19.2 mmols)of octanethiol in place of thiophenol, 4.91 g of6,7-dioctylthio-5,8-difluoroquinizarin dye (304)! (yield 90.5 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 6.

EXAMPLE 36

By following the procedure of Example 29 while using 1.74 g (19.2 mmols)of tert.-butylthiol in place of thiophenol, 4.02 g of 6,7-ditertiarybutylthio-5,8-difluoroquinizarin dye (305)! (yield 92.3 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 6.

EXAMPLE 37

By following the procedure of Example 29 while using 2.23 g (19.2 mmols)of cyclohexane thiol in place of thiophenol, 4.54 g of6,7-dicyclohexylthio-5,8-difluoroquinizarin dye (306)! (yield 93.6 mol%) was obtained. The physical properties of this dye and the analysesused for the identification of this compound are shown in Table 6.

EXAMPLE 38

By following the procedure of Example 29 while increasing the amount ofthiophenol to 4.24 g (38.5 mmols) and that of potassium fluoride to 2.68g (46.1 mmols) and changing the reaction time to 16 hours, 5.93 g5,6,7,8-tetraphenylthioquinizarin dye (307)! (yield 91.7 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 7.

EXAMPLE 39

By following the procedure of Example 38 while using 3.48 g (38.5 mmols)of n-butyl thiol in place of thiophenol, 5.09 g of5,6,7,8-tetrabutylthioquinizarin dye (308)! (yield 89.3 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 7.

EXAMPLE 40

In a four-neck flask of 500 cc in inner volume, 400 cc of octyl alcohol,3 g (6.18 mmols) of6-(p-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin dye (6)! and 0.347g (6.18 mmol) of potassium hydroxide were placed and left reacting at120° C. for about 5 hours. After the reaction, the reaction solution wastransferred into a separation funnel, combined with water, and shakentherein to effect separation. Then, the organic layer was distilled toexpel octyl alcohol. The solids remaining after the distillation weredried to obtain 3.55 g of6-(p-butoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin dye (36)!(yield 96.4 mol %). The physical properties of this dye and the analysesused for the identification of this compound are shown in Table 8.

EXAMPLE 41

By following the procedure of Example 40 while using 3 g (6.56 mmols) ofthe dye (4) in place of the dye (6) and further using 0.368 g (6.56mmols) of potassium hydroxide, 3.62 g of6-(m-ethoxycarbonylanilino)-7-octyloxy-5,8-difluoroquinizarin dye (34)!(yield 97.2 mol %) was obtained. The physical properties of this dye andthe analyses used for the identification of this compound are shown inTable 8.

EXAMPLE 42

By following the procedure of Example 40 while using 3 g (7.31 mmols) ofthe dye (10) in place of the dye (6) and further using 0.41 g (7.31mmols) of potassium hydroxide, 3.66 g of6-(p-cyanoanilino)-7-octyloxy-5,8-difluoroquinizarin dye (45)! (yield96.2 mol %) was obtained. The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table8.

EXAMPLE 43

By following the procedure of Example 40 while using 3 g (6.97 mmols) ofthe dye (12) in place of the dye (6) and further using 0.391 g (6.97mmols) of potassium hydroxide, 3.61 g of6-(p-nitroanilino)-7-octyloxy-5,8-difluoroquinizarin dye (41)! (yield95.8 mol %) was obtained. The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table8.

EXAMPLE 44

By following the procedure of Example 40 while using 3 g (6.80 mmols) ofthe dye (18) in place of the dye (6) and further using 0.381 g (6.80mmols) of potassium hydroxide, 3.56 g of6-(2,6-diethylanilino)-7-octyloxy-5,8-difluoroquinizarin dye (51)!(yield 94.9 mol %) was obtained. The physical properties of this dye andthe analyses used for the identification of this compound are shown inTable 8.

EXAMPLE 45

In a four-neck flask of 500 cc in inner volume, 400 cc of n-butanol, 3 g(6.18 mmols) of 6-(m-butoxycarbonylanilino)-5,7,8-trifluoroquinizarindye (7)!, and 0.694 g (12.4 mmols) of potassium hydroxide were placedand refluxed for reaction for about 6 hours. After the reaction, thereaction solution was transferred into a separation funnel, combinedwith water, and shaken therein to effect separation. Then, the organiclayer was distilled to expel n-butanol. The solids remaining after thedistillation were dried to obtain 3.3 g of a crude product. Then, thecrude product was refined by means of a column packed with silica gel(Wakogel C-200) to obtain 2.36 g of 6-(m-butoxy-carbonylanilino)-5(or8),7-dibutoxy-5-fluoroquinizarin dye (69)! (yield 64.3 mol %). Thephysical properties of this dye and the analyses used for theidentification of this compound are shown in Table 8.

EXAMPLE 46

By following the procedure of Example 45 while using 3 g (6.18 mmols) of6-(p-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin in place of6-(m-butoxycarbonylanilino)-5,7,8-trifluoroquinizarin and n-octylalcohol in place of n-butanol and changing the reaction temperature to120° C., 2.43 g of 6-(p-butoxycarbonylanilino)-5(or8),7-dioctyloxy-5-fluoroquinizarin dye (70)! (yield 55.7 mol %) wasobtained. The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 9.

EXAMPLE 47

In a four-neck flask of 500 cc in inner volume, 400 cc of aqua ammonia(29%) and 3 g (6.09 mmols) of 6,7-diphenylthio-5,8-difluoroquinizarindye (298)! were placed and left reacting at room temperature for about12 hours. After the reaction, the reaction solution was neutralized withconcentrated hydrochloric acid to induce separation of solids. Thesolids were separated by filtration, washed with water and dried toobtain 2.9 g of a crude product. Then, this crude product was refined bymeans of a column packed with silica gel (Wakogel C-200) to obtain 0.72g of 5-amino-6,7-diphenylthio-8-fluoroquinizarin dye (296)! (yield 24.1mol %). The physical properties of this dye and the analyses used forthe identification of this compound are shown in Table 9.

EXAMPLE 48

In a four-neck flask of 500 cc in inner volume, 400 cc of octyl alcohol,3 g (6.84 mmols) of 6-anilino-7-butylamino-5,8-difluoroquinizarin dye(229)!, and 0.384 g (6.84 mmols) of potassium hydroxide were placed andleft reacting at 120° C. for about 5 hours. After the reaction, thereaction solution was transferred into a separation funnel, combinedwith water, and shaken therein to effect separation. Then, the organiclayer was distilled to expel octyl alcohol. The solids remaining afterthe distillation were dried to obtain 3.63 g of6-anilino-7-butylamino-8(or 5)-octyloxy-5(or 8)-fluoroquinizarin dye(193)! (yield 96.7 mol %). The physical properties of this dye and theanalyses used for the identification of this compound are shown in Table9.

EXAMPLE 49

By following the procedure of Example 48 while using 3 g (5.88 mmols) ofthe dye (227) in place of the dye (229) and further using 0.33 g (5.88mmols) of potassium hydroxide, 3.44 g of6-(m-ethoxycarbonylanilino)-7-butylamino-8(or 5)-octyloxy-5(or8)-fluoroquinizarin dye (197)! (yield 94.3 mol %) was obtained. Thephysical properties of this dye and the analyses used for theidentification of this compound are shown in Table 9.

EXAMPLE 50

In a four-neck flask of 200 cc in inner volume, 100 g of aniline and 3 g(6.09 mmols) of 6,7-diphenylthio-5,8-difluoro-quinizarin dye (298)! wereplaced and left reacting at 150° C. for about 4 hours. After thereaction, the reaction solution was thrown into a mixture consisting ofabout 400 cc of acetone with about 500 cc of water and then acidifiedwith concentrated hydrochloric acid to induce separation of solids. Thesolids were separated by filtration, washed with water, and dried toobtain 3.2 g of a crude product. Then, this crude product was refined bymeans of a column packed with silica gel (Wakogel C-200) to obtain 1.21g of 5,8-dianilino-6,7-diphenylthioquinizarin dye (297)! (yield 31.2 mol%). The physical properties of this dye and the analyses used for theidentification of this compound are shown in Table 9.

EXAMPLES 51 AND 52

By following the procedures of Examples 20 and 21 while using 100 g of2,6-dichloroaniline in place of p-aminobenzonitrile and changing thereaction temperature to 200° C., 1.28 g of6-(2,6-dichloroanilino)-5,7,8-trifluoroquinizarin dye (22)! (yield 29.3mol %) and 0.43 g of 6,7-bis(2,6-dichloroanilino)-5,8-difluoroquinizarindye (138)! (yield 7.51 mol %) were obtained. The physical properties ofthe dye (22) and the analyses used for the identification of thiscompound are shown in Table 3 and the physical properties of the dye(138) and the analyses used for the identification of this compound inTable 5.

EXAMPLES 53 AND 54

By following the procedures of Examples 20 and 21 while using 100 g of2,6-diisopropyl aniline in place of p-aminobenzonitrile, 1.68 g of6-(2,6-diisopropylanilino)-5,7,8-trifluoroquinizarin dye (25)! (yield37.3 mol %) and 0.79 g of6,7-bis(2,6-diisopropylanilino)-5,8-difluoroquinizarin dye (139)! (yield13,1 mol %) were obtained. The physical properties of the dye (25) andthe analyses used for the identification of this compound are shown inTable 3 and the physical properties of the dye (139) and the analysesused for the identification of this compound in Table 5.

                                      TABLE 1                                     __________________________________________________________________________    λ max (nm)                                                                         Solubility                                                                              Melting                                                 ε   in  in methyl                                                                           point                Elemental analysis                 Dye No.                                                                            (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum    C (%)                                                                             H (%)                                                                             N (%)                                                                             F                                                                                Color               __________________________________________________________________________                                                              tone                (1)  533    ∘                                                                     Δ                                                                             185 385 (M.sup.+, 100)                                                                     Theoretical value                                                                     62.34                                                                             2.62                                                                              3.64                                                                              14.79                                                                            Magenta                  ε: 14800     366 (M.sup.+  -19, 60)                                                                 Measured value                                                                        62.29                                                                             2.66                                                                              3.69                                                                              14.82                  (4)  527    ∘                                                                     ∘                                                                       190 457 (M.sup.+, 100)                                                                     Theoretical value                                                                     60.40                                                                             3.09                                                                              3.06                                                                              12.46                                                                            Magenta                  ε: 15300     412 (M.sup.+  -45, 30)                                                                 Measured value                                                                        60.46                                                                             3.07                                                                              3.10                                                                              12.42                                            465 (M.sup.+  -92, 50)                              (5)  530    ⊚                                                                  ⊚                                                                    147 485 (M.sup.+, 100)                                                                     Theoretical value                                                                     61.86                                                                             3.74                                                                              2.89                                                                              11.74                                                                            Magenta                  ε: 8600      412 (M.sup.+  -73, 60)                                                                 Measured value                                                                        61.83                                                                             3.72                                                                              2.92                                                                              11.75                                            391 (M.sup.+  -94, 50)                              (6)  528    ∘                                                                     ∘                                                                       201 485 (M.sup.+, 90)                                                                      Theoretical value                                                                     61.86                                                                             3.74                                                                              2.89                                                                              11.74                                                                            Magenta                  ε: 17900     428 (M.sup.+  -57, 20)                                                                 Measured value                                                                        61.81                                                                             3.68                                                                              2.91                                                                              11.77                                            412 (M.sup.+  -73, 100)                             (8)  526    ∘                                                                     ∘                                                                       115 541 (M.sup.+, 100)                                                                     Theoretical value                                                                     64.32                                                                             4.84                                                                              2.59                                                                              10.52                                                                            Magenta                  ε: 17600     428 (M.sup.+  -113, 20)                                                                Measured value                                                                        64.30                                                                             4.86                                                                              2.63                                                                              10.51                  (10) 523    Δ                                                                           Δ                                                                             294 410 (M.sup.+, 100)                                                                     Theoretical value                                                                     61.47                                                                             2.21                                                                              6.83                                                                              13.89                                                                            Magenta                  ε: 20600     391 (M.sup.+  -19, 30)                                                                 Measured value                                                                        61.41                                                                             2.18                                                                              6.90                                                                              13.94                  __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    λ max (nm)                                                                         Solubility                                                                              Melting                                                 ε   in  in methyl                                                                           point                Elemental analysis                 Dye No.                                                                            (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum    C (%)                                                                             H (%)                                                                             N (%)                                                                             F                                                                                Color               __________________________________________________________________________                                                              tone                (12) 521    Δ                                                                           Δ                                                                             223 430 (M.sup.+, 100)                                                                     Theoretical value                                                                     55.83                                                                             2.11                                                                              6.51                                                                              13.25                                                                            Magenta                  ε: 16300     411 (M.sup.+  -19, 20)                                                                 Measured value                                                                        55.83                                                                             2.04                                                                              6.57                                                                              13.19                  (117)                                                                              533    ∘                                                                     ∘                                                                       170 365 (M.sup.+, 100)                                                                     Theoretical value                                                                     59.18                                                                             3.86                                                                              3.83                                                                              15.60                                                                            Magenta                  ε: 17900     322 (M.sup.+  -43, 100)                                                                Measured value                                                                        59.23                                                                             3.83                                                                              3.80                                                                              15.58                  (119)                                                                              536    ∘                                                                     ∘                                                                       167 391 (M.sup.+, 100)                                                                     Theoretical value                                                                     61.38                                                                             4.12                                                                              3.58                                                                              14.56                                                                            Magenta                  ε: 24500     348 (M.sup.+  -43, 30)                                                                 Measured value                                                                        61.41                                                                             4.08                                                                              3.50                                                                              14.57                                            308 (M.sup.+  -83, 30)                              (13) 540    ∘                                                                     ∘                                                                       184 441 (M.sup.+, 70)                                                                      Theoretical value                                                                     65.31                                                                             4.11                                                                              3.17                                                                              12.91                                                                            Magenta                  ε: 11900     426 (M.sup.+  -15, 100)                                                                Measured value                                                                        65.28                                                                             4.13                                                                              3.21                                                                              12.89                  (14) 557    ∘                                                                     ∘                                                                       240 415 (M.sup.+, 100)                                                                     Theoretical value                                                                     60.73                                                                             2.91                                                                              3.37                                                                              13.72                                                                            Purple                   ε: 15300     396 (M.sup.+  -19, 70)                                                                 Measured value                                                                        60.78                                                                             2.88                                                                              3.38                                                                              13.68                  __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    λ max (nm)                                                                        Solubility                                                                              Melting                                                  Dye ε                                                                            in  in methyl                                                                           point             Elemental analysis                     No. (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum C (%)                                                                             H (%)                                                                             N (%)                                                                             F (%)                                                                            Cl                                                                                Color               __________________________________________________________________________                                                              tone                (15)                                                                              542    ∘                                                                     ∘                                                                       --  415 (M.sup.+, 100)                                                                    Theoretical                                                                         60.73                                                                             2.91                                                                              3.37                                                                              13.72  Magenta                 ε: 10200     400 (M.sup.+  -15, 30)                                                                value                                                                         Measured                                                                            60.80                                                                             2.93                                                                              3.35                                                                              13.70                                                       value                                        (16)                                                                              532    ∘                                                                     ∘                                                                       222 415 (M.sup.+, 100)                                                                    Theoretical                                                                         60.73                                                                             2.91                                                                              3.37                                                                              13.72  Magenta                 ε: 16300     396 (M.sup.+  -19, 50)                                                                value                                                                         Measured                                                                            60.70                                                                             2.86                                                                              3.41                                                                              13.73                                                       value                                        (18)                                                                              528    ⊚                                                                  ∘                                                                       206 441 (M.sup.+, 100)                                                                    Theoretical                                                                         65.31                                                                             4.11                                                                              3.17                                                                              12.91  Magenta                 ε: 14200     422 (M.sup.+  -19, 30)                                                                value                                                                 407 (M.sup.+  -34, 80)                                                                Measured                                                                            65.25                                                                             4.08                                                                              3.22                                                                              12.90                                                       value                                        (22)                                                                              521    ⊚                                                                  ∘                                                                       222 454 (M.sup.+, 70)                                                                     Theoretical                                                                         52.89                                                                             1.78                                                                              3.08                                                                              12.55                                                                            15.61                                                                             Magenta                 ε: 9470      419 (M.sup.+  -35,                                                                    value                                                                 100)    Measured                                                                            52.93                                                                             1.75                                                                              3.13                                                                              12.51                                                                            15.55                                            456 (M.sup.+ +2, 20)                                                                  value                                        (25)                                                                              530    ⊚                                                                  ∘                                                                       --  469 (M.sup.+, 100)                                                                    Theoretical                                                                         66.50                                                                             4.73                                                                              2.98                                                                              12.15  Magenta                 ε: 12800     450 (M.sup.+  -19, 20)                                                                value                                                                 435 (M.sup.+  -34, 70)                                                                Measured                                                                            66.43                                                                             4.68                                                                              3.06                                                                              12.10                                                       value                                        (120)                                                                             648    Δ                                                                           Δ                                                                             297 458 (M.sup.+, 100)                                                                    Theoretical                                                                         68.12                                                                             3.52                                                                              6.11                                                                              8.29   Cyan                    ε: 19800     439 (M.sup.+  -19, 10)                                                                value                                                                 420 (M.sup.+  -38, 20)                                                                Measured                                                                            68.15                                                                             3.48                                                                              6.17                                                                              8.23                                                        value                                        (121)                                                                             644    ∘                                                                     ∘                                                                       247 602 (M.sup.+, 100)                                                                    Theoretical                                                                         63.79                                                                             4.01                                                                              4.65                                                                              6.31   Cyan                    ε: 20100     573 (M.sup.+  -29, 5)                                                                 value                                                                         Measured                                                                            63.87                                                                             3.93                                                                              4.70                                                                              6.28                                                        value                                        (122)                                                                             614    ∘                                                                     ∘                                                                       195 658 (M.sup.+, 100)                                                                    Theoretical                                                                         65.65                                                                             4.90                                                                              4.25                                                                              5.77   Blue                    ε: 14700     391 (M.sup.+  -267,                                                                   value                                                                 10)     Measured                                                                            65.61                                                                             4.90                                                                              4.30                                                                              5.71                                                        value                                        __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________                 Solubility                                                                              Melting                                                λ max (nm)                                                                          in  in methyl                                                                           point               Elemental analysis                 Dye No.                                                                            ε (in chloroform)                                                             toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum   C (%)                                                                             H (%)                                                                             N (%)                                                                             F                                                                                Color               __________________________________________________________________________                                                              tone                (126)                                                                              605    Δ                                                                           Δ                                                                             317 508 (M.sup.+, 100)                                                                     Theoretical value                                                                     66.14                                                                             2.78                                                                              11.02                                                                             7.47                                                                             Blue                     ε: 16600     489 (M.sup.+  -19, 5)                                                                  Measured value                                                                        66.09                                                                             2.81                                                                              11.00                                                                             7.52                   (130)                                                                              660    ∘                                                                     ∘                                                                       269 570 (M.sup.+, 100)                                                                     Theoretical value                                                                     71.56                                                                             5.65                                                                              4.91                                                                              6.66                                                                             Cyan                     ε: 26700     555 (M.sup.+  -15, 30)                                                                 Measured value                                                                        71.51                                                                             5.71                                                                              4.88                                                                              6.65                   (131)                                                                              661    ∘                                                                     ∘                                                                       276 518 (M.sup.+, 100)                                                                     Theoretical value                                                                     64.86                                                                             3.89                                                                              5.40                                                                              7.33                                                                             Cyan                     ε: 15600     484 (M.sup.+  -34, 20)                                                                 Measured value                                                                        64.91                                                                             3.90                                                                              5.33                                                                              7.29                   (132)                                                                              649    ∘                                                                     ∘                                                                       267 518 (M.sup.+, 100)                                                                     Theoretical value                                                                     64.86                                                                             3.89                                                                              5.40                                                                              7.33                                                                             Cyan                     ε: 13400     503 (M.sup.+  -15, 20)                                                                 Measured value                                                                        64.88                                                                             3.92                                                                              5.36                                                                              7.25                   (133)                                                                              651    ∘                                                                     ∘                                                                       242 518 (M.sup.+, 100)                                                                     Theoretical value                                                                     64.86                                                                             3.89                                                                              5.40                                                                              7.33                                                                             Cyan                     ε: 13400     499 (M.sup.+  -19, 20)                                                                 Measured value                                                                        64.93                                                                             3.82                                                                              5.39                                                                              7.36                   (227)                                                                              661    ∘                                                                     ∘                                                                       162 510 (M.sup.+, 100)                                                                     Theoretical value                                                                     63.53                                                                             4.74                                                                              5.49                                                                              7.44                                                                             Cyan                     ε: 21000     467 (M.sup.+  -43, 60)                                                                 Measured value                                                                        63.59                                                                             4.69                                                                              5.54                                                                              7.37                   __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________               Solubility                                                                              Melting                                                  Dye                                                                              λ max (nm)                                                                     in  in methyl                                                                           point             Elemental analysis                     No.                                                                              ε (in chloroform)                                                             toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum C (%)                                                                             H (%)                                                                             N (%)                                                                             F (%)                                                                            Cl                                                                                Color               __________________________________________________________________________                                                              tone                (228)                                                                            666     ∘                                                                     ∘                                                                       163 468 (M.sup.+, 100)                                                                    Theoretical                                                                         64.10                                                                             4.73                                                                              5.98                                                                              8.11   Cyan                   ε: 22800      425 (M.sup.+  -43, 60)                                                                value                                                                         Measured                                                                            64.04                                                                             4.69                                                                              6.03                                                                              8.09                                                        value                                        (229)                                                                            666     ∘                                                                     ∘                                                                       174 438 (M.sup.+, 100)                                                                    Theoretical                                                                         65.75                                                                             4.60                                                                              6.39                                                                              8.67   Cyan                   ε: 15300      395 (M.sup.+  -43, 70)                                                                value                                                                         Measured                                                                            65.80                                                                             4.58                                                                              6.45                                                                              8.64                                                        value                                        (137)                                                                            657     ⊚                                                                  ∘                                                                       262 570 (M.sup.+, 100)                                                                    Theoretical                                                                         71.56                                                                             5.65                                                                              4.91                                                                              6.66   Cyan                   ε: 30000      541 (M.sup.+  -29, 10)                                                                value                                                                         Measured                                                                            71.61                                                                             5.67                                                                              4.86                                                                              6.59                                                        value                                        (138)                                                                            630     ∘                                                                     ∘                                                                       260 596 (M.sup.+, 100)                                                                    Theoretical                                                                         52.38                                                                             2.03                                                                              4.70                                                                              6.37                                                                             23.79                                                                             Blue                   ε: 22300      561 (M.sup.+  -35, 30)                                                                value                                                                 598 (M.sup.+ +2, 30)                                                                  Measured                                                                            52.41                                                                             1.99                                                                              4.65                                                                              6.43                                                                             23.82                                                    value                                        (248)                                                                            614     ∘                                                                     ∘                                                                        83 471 (M.sup.+, 100)                                                                    Theoretical                                                                         66.22                                                                             7.27                                                                              8.91                                                                              4.03   Blue                   ε: 14900      428 (M.sup.+  -43, 10)                                                                value                                                                 414 (M.sup.+  -57, 80)                                                                Measured                                                                            66.19                                                                             7.31                                                                              8.87                                                                              3.99                                                        value                                        (139)                                                                            660     ⊚                                                                  ∘                                                                       --  626 (M.sup.+, 100)                                                                    Theoretical                                                                         72.81                                                                             6.44                                                                              4.47                                                                              6.07   Cyan                   ε: 26000      592 (M.sup.+  -34, 30)                                                                value                                                                         Measured                                                                            72.74                                                                             6.41                                                                              4.53                                                                              6.05                                                        value                                        __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    λ max (nm)                                                                         Solubility                                                                              Melting                                                 ε   in  in methyl                                                                           point                Elemental analysis                 Dye No.                                                                            (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum    C (%)                                                                             H (%)                                                                             N (%)                                                                             F                                                                                Color               __________________________________________________________________________                                                              tone                (305)                                                                              506    ⊚                                                                  ⊚                                                                    --  453 (M.sup.+, 10)                                                                      Theoretical value                                                                     58.39                                                                             4.90                                                                              14.17                                                                             8.40                                                                             Orange                   ε: 15300     396 (M.sup.+  -57, 100)                                                                Measured value                                                                        58.43                                                                             4.81                                                                              14.26                                                                             8.39                                             339 (M.sup.+  -114,                                                           20)                                                 (303)                                                                              506    ∘                                                                     ∘                                                                       --  508 (M.sup.+, 100)                                                                     Theoretical value                                                                     61.40                                                                             5.94                                                                              12.61                                                                             7.47                                                                             Orange                   ε: 11300     589 (M.sup.+  -19, 20)                                                                 Measured value                                                                        61.35                                                                             5.90                                                                              12.71                                                                             7.45                   (304)                                                                              504    ∘                                                                     ∘                                                                       --  564 (M.sup.+, 100)                                                                     Theoretical value                                                                     63.80                                                                             6.78                                                                              11.35                                                                             6.73                                                                             Orange                   ε: 14600     545 (M.sup.+  -19, 5)                                                                  Measured value                                                                        63.87                                                                             6.81                                                                              11.31                                                                             6.69                   (306)                                                                              508    ⊚                                                                  ∘                                                                       --  504 (M.sup.+, 90)                                                                      Theoretical value                                                                     61.89                                                                             5.19                                                                              12.71                                                                             7.53                                                                             Orange                   ε: 14000     338 (M.sup.+  -116,                                                                    Measured value                                                                        61.94                                                                             5.21                                                                              12.66                                                                             7.49                                             100)                                                (298)                                                                              489    ⊚                                                                  ∘                                                                       --  429 (M.sup.+, 60)                                                                      Theoretical value                                                                     63.41                                                                             2.87                                                                              13.02                                                                             7.71                                                                             Orange                   ε: 12700      77 (M.sup.+  -352,                                                                    Measured value                                                                        63.49                                                                             2.91                                                                              12.98                                                                             7.67                                             100)                                                __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    λ max (nm)                                                                       Solubility                                                                              Melting             Elemental analysis                    Dye                                                                              ε                                                                            in  in methyl                                                                           point               C  H  N  S  F  O                      No.                                                                              (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum   (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              Color               __________________________________________________________________________                                                              tone                (301)                                                                            514    ∘                                                                     ∘                                                                       --  524 (M.sup.+, 100)                                                                     Theoretical                                                                          59.54                                                                            2.69  12.22                                                                            7.24  Cinnabar               ε: 12900     505 (M.sup.+  -19, 10)                                                                 value                    red                                         398 (M.sup.+  -126, 50)                                                                Measured value                                                                       59.62                                                                            2.71  12.18                                                                            7.21                      (302)                                                                            504    ∘                                                                     ∘                                                                       --  552 (M.sup.+, 100)                                                                     Theoretical                                                                          60.86                                                                            3.28  11.60                                                                            6.88  Cinnabar               ε: 15100     533 (M.sup.+  -19, 10)                                                                 value                    red                                         412 (M.sup.+  -140, 20)                                                                Measured value                                                                       60.93                                                                            3.29  11.57                                                                            6.79                      (299)                                                                            510    Δ                                                                           Δ                                                                             --  724 (M.sup.+, 20)                                                                      Theoretical                                                                          46.42                                                                            0.83  8.85                                                                             26.22 Cinnabar               ε: 12600     686 (M.sup.+  -38, 20)                                                                 value                    red                                         667 (M.sup.+  -82, 100)                                                                Measured value                                                                       46.33                                                                            0.77  8.93                                                                             26.24                     (300)                                                                            521    Δ                                                                           Δ                                                                             --  686 (M.sup.+, 100)                                                                     Theoretical                                                                          48.99                                                                            0.59                                                                             4.08                                                                             9.34                                                                             27.68 Cinnabar               ε: 13200     642 (M.sup.+  -44, 40)                                                                 value                    red                                         499 (M.sup.+  -187, 70)                                                                Measured value                                                                       49.08                                                                            0.63                                                                             4.12                                                                             9.27                                                                             27.56                     (308)                                                                            530    ⊚                                                                  ∘                                                                       --  592 (M.sup.+, 30)                                                                      Theoretical                                                                          60.78                                                                            6.80  21.63 10.79                                                                            Magenta                ε: 11100     535 (M.sup.+  -57, 50)                                                                 value                                                                478 (M.sup.+  -114,                                                                    Measured value                                                                       60.77                                                                            6.71  21.67 10.85                                          100)                                                  (307)                                                                            495    ∘                                                                     ∘                                                                       --  673 (M.sup.+, 100)                                                                     Theoretical                                                                          67.83                                                                            3.60  19.06 9.51                                                                             Brown                  ε: 12600      77 (M.sup.+  -596, 30)                                                                value                                                                         Measured value                                                                       67.80                                                                            3.65  19.01 9.54                   __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    λ max (nm)                                                                         Solubility                                                                              Melting                                                 ε   in  in methyl                                                                           point                Elemental analysis                 Dye No.                                                                            (in chloroform)                                                                      toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum    C (%)                                                                             H (%)                                                                             N (%)                                                                             F                                                                                Color               __________________________________________________________________________                                                              tone                (34) 531    ⊚                                                                  ⊚                                                                    131 567 (M.sup.+, 70)                                                                      Theoretical value                                                                     65.60                                                                             5.50                                                                              2.47                                                                              6.69                                                                             Magenta                  ε: 12400     454 (M.sup.+  -113,                                                                    Measured value                                                                        65.67                                                                             5.50                                                                              2.51                                                                              6.62                                             100)                                                (36) 534    ⊚                                                                  ⊚                                                                    101 595 (M.sup.+, 80)                                                                      Theoretical value                                                                     66.54                                                                             5.92                                                                              2.35                                                                              6.38                                                                             Magenta                  ε: 12700     482 (M.sup.+  -113,                                                                    Measured value                                                                        66.56                                                                             5.88                                                                              2.32                                                                              6.36                                             100)                                                (41) 524    ⊚                                                                  ⊚                                                                    116 540 (M.sup.+, 70)                                                                      Theoretical value                                                                     62.22                                                                             4.85                                                                              5.18                                                                              7.03                                                                             Magenta                  ε: 13200     427 (M.sup.+  -113,                                                                    Measured value                                                                        62.30                                                                             4.87                                                                              5.15                                                                              6.68                                             100)                                                (45) 524    ⊚                                                                  ⊚                                                                    127 520 (M.sup.+, 50)                                                                      Theoretical value                                                                     66.92                                                                             5.03                                                                              5.38                                                                              7.30                                                                             Magenta                  ε: 15400     407 (M.sup.+  -113,                                                                    Measured value                                                                        66.89                                                                             5.01                                                                              5.41                                                                              7.28                                             100)                                                (51) 563    ⊚                                                                  ⊚                                                                    --  551 (M.sup.+, 100)                                                                     Theoretical value                                                                     69.68                                                                             6.39                                                                              2.54                                                                              6.89                                                                             Purple                   ε: 11400     438 (M.sup.+  -113,                                                                    Measured value                                                                        69.74                                                                             6.40                                                                              2.49                                                                              6.93                                             80)                                                 (69) 538    ⊚                                                                  ⊚                                                                    --  593 (M.sup.+, 100)                                                                     Theoretical value                                                                     66.77                                                                             6.11                                                                              2.36                                                                              3.20                                                                             Magenta                  ε: 15000     536 (M.sup.+  -57, 60)                                                                 Measured value                                                                        66.80                                                                             6.10                                                                              2.39                                                                              3.17                   __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________               Solubility                                                                              Melting            Elemental analysis                    Dye                                                                              λ max (nm)                                                                     in  in methyl                                                                           point              C  H  N  S  F  O                      No.                                                                              ε (in chloroform)                                                             toluene                                                                           ethyl ketone                                                                        (°C.)                                                                      Mass spectrum  (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              (%)                                                                              Color               __________________________________________________________________________                                                              tone                 (70)                                                                            538     ⊚                                                                  ⊚                                                                    --  705 (M.sup.+, 100)                                                                    Theoretical                                                                          69.77                                                                            7.43                                                                             1.98  2.69  Magenta                ε: 12800      592 (M.sup.+  -113,                                                                   value                                                                 10)     Measured value                                                                       69.75                                                                            7.44                                                                             1.97  2.74                                               479 (M.sup.+  226, 20)                               (296)                                                                            542     ∘                                                                     ∘                                                                       --  489 (M.sup.+, 100)                                                                    Theoretical                                                                          63.79                                                                            3.29                                                                             2.86                                                                             13.10                                                                            3.88  Purple                 ε: 12300       77 (M.sup.+  -412,                                                                   value                                                                 30)     Measured value                                                                       63.75                                                                            3.30                                                                             2.84                                                                             13.13                                                                            3.89                      (193)                                                                            668     ⊚                                                                  ⊚                                                                    --  548 (M.sup.+, 100)                                                                    Theoretical                                                                          70.05                                                                            6.80                                                                             5.11  3.46  Cyan                   ε: 15300      529 (M.sup.+  -19, 10)                                                                value                                                                 435 (M.sup.+  113, 30)                                                                Measured value                                                                       70.08                                                                            6.79                                                                             5.09  3.47                      (197)                                                                            665     ⊚                                                                  ⊚                                                                    --  620 (M.sup.+, 100)                                                                    Theoretical                                                                          67.73                                                                            6.66                                                                             4.51  3.06  Cyan                   ε: 13800      507 (M.sup.+  -113,                                                                   value                                                                 20)     Measured value                                                                       67.69                                                                            6.68                                                                             4.48  3.10                      (297)                                                                            692     ∘                                                                     ∘                                                                       --  638 (M.sup.+, 70)                                                                     Theoretical                                                                          71.45                                                                            4.10                                                                             4.39                                                                             10.04 10.02                                                                            Cyan                   ε: 15900       77 (M.sup.+  -561,                                                                   value                                                                 100)    Measured value                                                                       71.52                                                                            4.05                                                                             4.42                                                                             9.98  10.03                  __________________________________________________________________________

EXAMPLE 55

In a four-neck flask of 100 cc in inner volume, 50 cc of acetonitrile,0.5 g (1.09 mmols) of6-(m-ethoxycarbonylanilino)-5,7,8-trifluoroquinizarin, 0.1 g (1.72mmols) of potassium fluoride, and 0.12 g (1.09 mmols) of thiophenol wereplaced and refluxed for reaction for about 2.5 hours. After thereaction, the reaction solution was filtered to remove potassiumfluoride and then the organic layer was distilled to expel acetonitrile.The solids remaining after the distillation were dried to obtain 0.56 gof 6-(m-ethoxycarbonylanilino)-7-(phenylthio)-5,8-difluoroquinizarin dye(115)! (yield 91.9 mol %). The physical properties of this dye and theanalyses used for the identification of this compound are shown below.

Visible absorption spectrum (in chloroform):

λmax 540 nm (ε: 17000)

Mass spectrum:

m/e=547 (M⁺, 100)

m/e=501 (M⁺ -46, 20)

    ______________________________________                                        Elementary analyses:                                                                  C (%)  H (%)    N (%)    S (%) F (%)                                  ______________________________________                                        Theoretical value                                                                       63.61    3.50     2.56   5.84  6.95                                 Measured value                                                                          63.48    3.43     2.67   5.78  6.97                                 ______________________________________                                    

EXAMPLE 56

In a four-neck flask of 100 cc in inner volume, 50 cc ofα-chloronaphthalene, 0.5 g (0.80 mmol) of6,7-bis(2,6-diisopropylanilino)-5,8-difluoroquinizarin, 0.07 g (1.20mmols) of potassium fluoride, and 0.58 g (4.0 mmols) of octanethiol wereplaced and refluxed for reaction for about 24 hours. After the reaction,the reaction solution was filtered to remove potassium fluoride and thenthe organic layer was distilled to expel α-chloronaphthalene. The solidsconsequently obtained were dried to obtain 0.57 g of a crude product.Then, the crude product was refined by means of a column packed withsilica gel (Wakogel C-200) to obtain 0.38 g of6,7-bis(2,6-diisopropylanilino)-5-(octylthio)-8-fluoroquinizarin dye(232)! (yield 63.3 mol %). The physical properties of this dye and theanalyses used for the identification of this compound are shown below.

Visible absorption spectrum (in chloroform):

λmax 664.0 nm (ε: 17000)

709.5 nm (ε: 21700)

Mass spectrum:

m/e=753 (M⁺, 60)

m/e=607 (M⁺ -146, 70)

m/e=592 (M⁺ -161, 80)

    ______________________________________                                        Elementary analyses:                                                                  C (%)  H (%)    N (%)    S (%) F (%)                                  ______________________________________                                        Theoretical value                                                                       73.37    7.63     3.72   4.20  2.52                                 Measured value                                                                          73.30    7.70     3.77   4.15  2.53                                 ______________________________________                                    

Melting point:

254.3° C.

EXAMPLE 57

In a four-neck flask of 50 cc in inner volume, 1 g (3.22 mmols) of6-(hydroxy)-5,7,8-trifluoroquinizarin and 20 ml of 2,6-diisopropylaniline were placed and left reacting at 140° C. for about 3 hours.After the reaction, the reaction solution was thrown into a mixtureconsisting of about 200 cc of acetone with about 200 cc of water andthen acidified with concentrated hydrochloric acid to induce separationof solids. The solids were separated by filtration, washed with water,and dried to obtain 1.6 g of a crude product. Then, this crude productwas refined by means of a column packed with silica gel (Wakogel C2-00)to obtain 0.7 g of 6,8(or 5)-bis(2,6-diisopropylanilino)-7-hydroxy-5(or8)-fluoroquinizarin dye (231)! (yield 34.8 mol %). The physicalproperties of this dye and the analyses used for the identification ofthis compound are shown below.

Visible absorption spectrum (in ethyl cellosolve):

λmax 644.5 nm (ε: 33400)

595.5 nm

Mass spectrum:

m/e=624 (M⁺, 100)

m/e=607 (M⁺ -17, 30)

    ______________________________________                                        Elementary analyses:                                                                     C (%) H (%)     N (%)   F (%)                                      ______________________________________                                        Theoretical value                                                                          73.04   6.62      4.49  3.04                                     Measured value                                                                             73.30   6.63      4.48  3.08                                     ______________________________________                                    

EXAMPLE 58

In a four-neck flask of 500 cc in inner volume, 3.0 g (9.61 mmols) of5,6,7,8-tetrafluoroquinizarin, 3.75 g (19.2 mmols) of sodium sulfanilateand 350 ml of butanol were placed and refluxed for reaction for about 10hours. After the reaction, the reaction solution was filtered to removebutanol, to obtain 4.78 g of a crude product. Then, this crude productwas refined by means of a column packed with silica gel (Wakogel C2-00)to obtain 1.25 g of 6-(p-sodium sulfonateanilino)-5,7,8-trifluoroquinizarin dye (27)! (yield 26.7 mol %). Thephysical properties of this dye and the analyses used for theidentification of this compound are shown below.

Visible absorption spectrum (in methanol):

λmax 521.5 nm (ε: 10600)

    ______________________________________                                        Elementary analyses:                                                                  C (%) H (%)   N (%)   F (%) S (%)                                                                              Ash (%)                              ______________________________________                                        Theoretical value                                                                       49.28   1.85    2.88  11.70 6.57 4.72                               Measured value                                                                          49.26   1.89    2.84  11.75 6.51 4.70                               ______________________________________                                    

EXAMPLE 59

In a four-neck flask of 500 cc in inner volume, 0.7 g (1.54 mmols) of6-(2,6-dichloroanilino)-5,7,8-trifluoroquinizarin, 3.0 g (31.9 mmols) ofphenol, 350 ml of isopropyl alcohol, and 0.0863 g (1.54 mmols) ofpotassium hydroxide were placed and refluxed for reaction for about 3hours. After the reaction, the reaction solution was distilled to expelisopropyl alcohol. The distillate was dissolved in toluene, transferredinto a separation funnel, combined with an aqueous sodium hydroxidesolution, and shaken to effect separation. Then, the organic layer wasdistilled to expel toluene. The solids consequently obtained were driedto obtain 0.772 g of6-(2,6-dichloroanilino)-7-phenoxy-5,8-difluoroquinizarin dye (110)!(yield 94.8 mol %). The physical properties of this dye and the analysesused for the identification of this compound are shown below.

Visible absorption spectrum (in chloroform):

λmax 521.0 nm (ε: 17900)

Mass spectrum:

m/e=529 (M⁺, 80)

m/e=492 (M⁺ -37, 100)

    ______________________________________                                        Elementary analyses:                                                                  C (%)  H (%)    N (%)    F (%) Cl (%)                                 ______________________________________                                        Theoretical value                                                                       59.11    2.48     2.65   7.18  13.42                                Measured value                                                                          59.07    2.49     2.66   7.15  13.45                                ______________________________________                                    

Melting point:

182.9° C.

EXAMPLE 60

In a four-neck flask of 100 cc in inner volume, 70 g of 2,6-isopropylaniline and 3 g (11.6 mmols) of 6-fluoroquinizarin were placed and leftreacting at 230° C. for about 3 hours. After the reaction, the reactionsolution was thrown into a mixture consisting of about 400 cc of acetonewith about 500 cc of water and then acidified with concentratedhydrochloric acid to induce separation of solids. The solids wereseparated by filtration, washed with water, and dried to obtain 5.4 g ofa crude product. Then, this crude product was refined by means of acolumn packed with silica gel (Wakogel C-200) to obtain 4.1 g of6-(2,6-isopropylanilino) quinizarin dye (99)! (yield 84.4 mol %). Thephysical properties of this dye and the analyses used for theidentification of this compound are shown below.

Visible absorption spectrum (in toluene):

λmax 560 nm (ε: 14850)

Mass spectrum:

m/e=415 (M⁺, 60)

m/e=400 (M⁺ -25, 100)

    ______________________________________                                        Elementary analyses:                                                                     C (%) H (%)     N (%)   O (%)                                      ______________________________________                                        Theoretical value                                                                          75.16   6.06      3.37  15.40                                    Measured value                                                                             75.07   6.10      3.31  15.51                                    ______________________________________                                    

Solubility

Not less than 3% by weight in toluene.

EXAMPLE 61

In a four-neck flask of 100 cc in inner volume, 70 g of dichloro anilineand 3 g (11.6 mmols) of 6-fluoroquinizarin were placed and left reactingat 250° C. for about 5 hours. After the reaction, the reaction solutionwas thrown into a mixture consisting of about 400 cc of acetone withabout 500 cc of water and then acidified with concentrated hydrochloricacid to induce separation of solids. The solids were separated byfiltration, washed with water, and dried to obtain 3.8 g of a crudeproduct. Then, this crude product was refined by means of a columnpacked with silica gel (Wakogel C-200) to obtain 2.6 g of6-(2,6-dichloroanilino) quinizarin dye (102)! (yield 56.0 mol %). Thephysical properties of this dye and the analyses used for theidentification of this compound are shown below.

Visible absorption spectrum (in toluene):

λmax 516 nm (ε: 15600)

Mass spectrum:

m/e=400 (M⁺, 60)

m/e=399 (M⁺, 70)

m/e=364 (M⁺ -36, 100)

    ______________________________________                                        Elementary analyses:                                                                     C (%) H (%)     N (%)   Cl (%)                                     ______________________________________                                        Theoretical value                                                                          60.02   2.77      3.50  17.72                                    Measured value                                                                             60.15   2.71      3.45  17.97                                    ______________________________________                                    

Solubility

Not less than 3% by weight in toluene.

EXAMPLE 62

In a four-neck flask of 50 cc in inner volume, 5 g (16.1 mmols) of5,6,7,8-tetrafluoroquinizarin and 25 ml of 2,6-diisopropyl aniline wereplaced and left reacting at 180° C. for about 24 hours. After thereaction, the reaction solution was thrown into a mixture consisting ofabout 200 cc of acetone with about 200 cc of water and then acidifiedwith concentrated hydrochloric acid to induce separation of solids. Thesolids were separated by filtration, washed with water, and dried toobtain 6.5 g of a crude product. Then, this crude product was refined bymeans of a column packed with silica gel (Wakogel C-200) to obtain 1.04g of 5,6,7-tris(2,6-diisopropylanilino)-8-fluoroquinizarin dye (245)!(yield 8.1 mol %). The physical properties of this dye and the analysesused for the identification of this compound are shown below.

Visible absorption spectrum (in ethyl cellosolve):

λmax 698.5 nm (ε: 29200)

643.0 nm

Mass spectrum:

m/e=622 (M⁺, -162 100)

m/e=606 (M⁺, -178 30)

    ______________________________________                                        Elementary analyses:                                                                     C (%) H (%)     N (%)   F (%)                                      ______________________________________                                        Theoretical value                                                                          76.59   7.46      5.36  2.42                                     Measured value                                                                             76.61   7.42      5.31  2.48                                     ______________________________________                                    

EXAMPLE 63

Four (4) parts of 6-anilino-7-butylamino-5(or 8)-octyloxy-8(or5)-fluoroquinizarin dye (193)! and 97 parts of a styrene-acrylic estercopolymer (produced by Sanyo Chemical Industries Co., Ltd. and marketedunder trademark designation of "Himer TB1000F") were fused and kneadedwith hot rolls at a temperature of about 150° C. The resultant moltenmixture was cooled, coarsely pulverized with a hammer mill, and thenfinely pulverized with an air jet type fine pulverizer. The fine powderconsequently obtained was classified to separate a part having particlediameters in the range of 3 to 20 μm. The separated part of the powderwas used as a toner.

Four parts of this toner and 100 parts of a carrier (produced by coatinga ferrite powder having particle diameters in the range of 50 to 150 μmwith a silicone resin) were uniformly mixed to prepare a developer. Whena given image was copied in a xerographic copying device (produced byRicoh Company Limited and marketed under product code of "FT-4060")using this developer, clear cyan images perfectly free from fogging wereobtained. The copied images were tested for lightfastness with a xenonlamp lightfastness tester (produced by Heraeus Corp. and marketed undertrademark designation of "SUNTEST CPS") (black panel temperature 63° C.)and subjected to measurement of color density with a densitometer(produced by McBeth Corp. of U.S. and marketed under product code of"RD-914") to rate ratio of retention of color density after 100 hours'standing. The images showed a ratio of retention of not less than 92%,based on the initial color density taken as 100%. The results indicatethat the developer possessed ideal lightfastness.

EXAMPLES 64 TO 75

Toners were prepared by following the procedure of Example 63 whileusing the dye shown in Table 10 instead and were tested forlightfastness by the same copying test. In the test, clear cyan imagesfree from fogging were obtained similarly to those obtained in Example63. The copied images were tested for lightfastness. The results areshown in Table 10. They indicate that all the copied images showedratios of retention of color density invariably exceeding 90%.

EXAMPLES 76 TO 88

Toners were prepared by following the procedure of Example 63 whileusing the dye shown in Table 10 instead and were tested forlightfastness by the same copying test. In the test, clear magentaimages free from fogging were obtained similarly to those obtained inExample 63. The copied images were tested for lightfastness. The resultsare shown in Table 10. They indicate that all the copied images showedratios of retention of color density invariably exceeding 90%.

                  TABLE 10                                                        ______________________________________                                                            Ratio of reteinsion                                       Example  Dye No.    of color density (%)                                                                       Color tone                                   ______________________________________                                        63       (193)      92           Cyan                                         64       (197)      91           Cyan                                         65       (196)      92           Cyan                                         66       (156)      95           Cyan                                         67       (157)      96           Cyan                                         68       (137)      95           Cyan                                         69       (139)      94           Cyan                                         70       (158)      92           Cyan                                         71       (159)      93           Cyan                                         72       (160)      94           Cyan                                         73       (161)      95           Cyan                                         74       (162)      93           Cyan                                         75       (163)      92           Cyan                                         76        (33)      91           Magenta                                      77        (36)      92           Magenta                                      78        (41)      95           Magenta                                      79        (45)      94           Magenta                                      80        (51)      90           Magenta                                      81        (65)      93           Magenta                                      82        (69)      94           Magenta                                      83        (68)      95           Magenta                                      84        (72)      93           Magenta                                      85        (75)      94           Magenta                                      86        (70)      91           Magenta                                      87        (22)      94           Magenta                                      88       (102)      92           Magenta                                      ______________________________________                                    

EXAMPLE 89

(1) Method for preparation of ink composition

Cyan dye (193) 3 parts

Polyvinyl butyral resin (produced by Sekisui Chemical Co., Ltd. andmarketed 4 parts under product code of "BLS-S")

Methylethyl ketone 47 parts

Toluene 47 parts

An ink composition was prepared by forming a dye blend composed of thecomponents shown above and subjecting the dye blend and glass beads to amixing treatment by the use of a paint shaker for about 30 minutes.

(2) Method for manufacture of transfer sheet

The ink was applied in such an amount as to form a dry layer about 1 μmin thickness to the rear face of a polyethylene terephthalate film(produced by Unitika Ltd. and marketed under trademark designation of"EMBLET") having a thickness of 5.7 μm and having undergone aheatproofing treatment with a silicone graft copolymer (about 1 μm)(produced by Nippon Shokubai Co., Ltd.) and the applied layer of the inkwas dried.

(3) Material to which images were transferred

Print papers for Mitsubishi video print pack (produced by MitsubishiElectric Corp. and marketed under product code of "CK-10P") were used asmaterials to which images were to be transferred.

(4) Transfer recording

Transfer recording was effected by superposing the inked surface of atransfer sheet on the dye-receiving surface of the print paper mentionedabove and operating a thermal head on the rear surface side of thetransfer sheet under the conditions of 10 V of voltage applied to thehead and 4.0 m.sec. of printing time. The results were as shown in Table11. The color density was measured by the use of a densitometer(produced by McBeth Corp. of U.S. and marketed under product code of"RD-914").

(5) Lightfastness

The recorded images were tested for lightfastness by the use of a xenonlamp lightfastness tester (produced by Heraeus Corp. and marketed undertrademark designation of "SUNTEST CPS") (black panel temperature 63°C.). The results of the test were rated by the ratio of retention ofcolor density after 100 hours' standing. The results were as shown inTable 11.

(6) Stability in storage

The recorded images obtained as described above were left standing in anatmosphere kept at 50° C. for 50 hours and, after the standing, wereexamined to determine the presence or absence of change caused on theimages owing to the standing. The results were as shown in Table 11. Theimages were found to have retained their clearness intact. When a whitepaper was rubbed against the images, it was not stained with the ink.This fact indicates that the ink excelled in stability in storage.

EXAMPLES 90 TO 100

Ink compositions were prepared, transfer sheets produced, and transferrecording carried out by following the procedure of Example 89 whileusing the dye shown in Table 11 instead. The results were as shown inTable 11. The recorded images were tested for lightfastness and then forstability in storage in the same manner as in Example 89. The resultswere as shown in Table 11.

                  TABLE 11                                                        ______________________________________                                                        Color                                                                         development      Light-                                                                              Stability in                           Example                                                                              Dye No.  strength  Color tone                                                                           fastness                                                                            stroage                                ______________________________________                                        89     (193)    2.48      Cyan   ◯                                                                       Good                                   90     (197)    2.43      Cyan   ◯                                                                       Good                                   91     (196)    2.33      Cyan   ⊚                                                                    Good                                   92     (156)    2.28      Cyan   ⊚                                                                    Good                                   93     (137)    2.39      Cyan   ⊚                                                                    Good                                   94     (139)    2.42      Cyan   ◯                                                                       Good                                   95     (141)    2.35      Cyan   ⊚                                                                    Good                                   96     (158)    2.43      Cyan   ◯                                                                       Good                                   97     (159)    2.36      Cyan   ◯˜Δ                                                         Good                                   98     (183)    2.14      Cyan   ⊚                                                                    Good                                   99     (160)    2.34      Cyan   ◯                                                                       Good                                   100    (162)    2.37      Cyan   ◯                                                                       Good                                   ______________________________________                                         Lightfastness                                                                 ⊚: Ratio of retension of color density is not less than        80%.                                                                          ◯: Ratio of retension of color density is not less than 70%.      ◯˜Δ: Ratio of retension of color density is not       less than 60%.                                                           

EXAMPLES 101 TO 113

Ink compositions were prepared, transfer sheets produced, and transferrecording carried out by following procedure of Example 89 while usingthe dyes shown in Table 12 instead. The results were as shown in Table12. The recorded images were tested for lightfastness and then stabilityin storage in the same manner as in Example 89. The results were asshown in Table 12.

                  TABLE 12                                                        ______________________________________                                                        Color                                                                         development      Light-                                                                              Stability in                           Example                                                                              Dye No.  strength  Color tone                                                                           fastness                                                                            stroage                                ______________________________________                                        101    (33)     2.42      Magenta                                                                              ◯                                                                       Good                                   102    (36)     2.39      Magenta                                                                              ◯                                                                       Good                                   103    (41)     2.61      Magenta                                                                              ◯                                                                       Good                                   104    (45)     2.54      Magenta                                                                              ⊚                                                                    Good                                   105    (51)     2.58      Magenta                                                                              ⊚                                                                    Good                                   106    (65)     2.52      Magenta                                                                              ◯˜Δ                                                         Good                                   107    (69)     2.63      Magenta                                                                              ◯                                                                       Good                                   108    (68)     2.23      Magenta                                                                              ⊚                                                                    Good                                   109    (72)     2.39      Magenta                                                                              ⊚                                                                    Good                                   110    (75)     2.44      Magenta                                                                              ⊚                                                                    Good                                   111    (70)     2.33      Magenta                                                                              ◯                                                                       Good                                   112    (22)     2.25      Magenta                                                                              ⊚                                                                    Good                                   113    (102)    2.12      Magenta                                                                              ⊚                                                                    Good                                   ______________________________________                                         Lightfastness                                                                 ⊚: Ratio of retension of color density is not less than        80%.                                                                          ◯: Ratio of retension of color density is not less than 70%.      ◯˜Δ: Ratio of retension of color density is not       less than 60%.                                                           

EXAMPLE 114

On a substrate of polycarbonate resin measuring 1.2 mm in thickness, 120mm in outside diameter, and 15 mm in inside diameter and containing aspiral guide groove 80 nm in depth and 1.6 μm in pitch, a coatingsolution prepared by dissolving the compound (245) mentioned above at aconcentration of 6% in methyl cellosolve was deposited in the form of afilm of 120 nm in thickness by the use of a spin coater. Then, on theapplied film of the coating solution, gold was vacuum deposited in athickness of 70 nm. Further, a protective film of an ultraviolet lightcuring resin was superposed on the coat of gold to complete an opticalrecording medium. The optical recording medium thus obtained was testedfor reflectance in the wavelength zone of 770 nm to 800 nm. It was foundto have a reflectance of 71%. This fact indicates that the opticalrecording medium possessed stable optical characteristics.

On this optical recording medium, an EMF signal was recordedsuccessfully with a semiconductor laser of a wavelength of 780 nm at anoutput of 6.5 mW and a linear velocity of 1.4 m/s. The analysis of thesignal thus obtained revealed that the level of this signal sufficed foreffective regeneration with a commercially available CD player.

EXAMPLES 115 TO 122

Optical recording media were obtained by following the procedure ofExample 114 while using the compound (232), the compound (233), thecompound (234), the compound (239), the compound (240), and the compound(241) in place of the compound (245) and they were tested forreflectance in the same manner as in Example 114. The reflectances theyshowed were invariably not less than 70%, indicating that they possessedstable optical characteristics.

On these optical recording media, an EMF signal was recordedsuccessfully with a semiconductor laser of a wavelength of 780 nm at anoutput of 6.5 mW and a linear velocity of 1.3 m/s. The analysis of thesignals thus recorded revealed that their levels sufficed for effectiverecording with a commercially available CD player.

EXAMPLES 123 TO 128

(1) Preparation of recording ink

Recording inks were prepared by thoroughly mixing and dissolving thecomponents of varying compositions shown below in Table 13 and coolingthe resultant blends.

(2) Recording

In a commercially available solid ink grade ink jet printer which waspartly modified for the sake of use herein, ink jet recording wascarried out using the recording ink produced as described above. Therecorded images consequently obtained were invariably very clear, richin contrast, and satisfactory in color tone. They were tested forlightfastness by the following method.

(3) Evaluation of lightfastness

The recorded images were tested for lightfastness by the use of a xenonlightfastness tester (produced by Heraeus Corp. and marketed undertrademark designation of "SUNTEST CPS") (black panel temperature 63° C.)and subjected to measurement of color density by the use of adensitometer (produced by McBeth Corp. of U.S. and marketed underproduct code of "RD-914"). The results of the measurement were rated bythe ratio of retention of color density after 100 hours' standing. Theratios of retention of color density were invariably not less than 90%,based on the initial density taken as 100%. This fact indicates that therecording inks excelled in lightfastness.

The results were as shown in Table 13.

                  TABLE 13                                                        ______________________________________                                                     Example                                                                       123  124    125    126  127  128                                 ______________________________________                                        Oleic acid                   25             25                                Benzyl ether                 60             60                                Japan wax             98               98                                     Acrylate - type synthetic wax                                                                98            13   98        13                                (Produced by Nippon                                                           Shokubai Co., Ltd. and                                                        marketed under                                                                product code "CX-ST100")                                                      Dye (22)        2      2      2                                               Dye (139)                          2    2    2                                Lightfastness  95%    93%    92%  93%  92%  94%                               ______________________________________                                    

EXAMPLE 129

A color filter was produced by preparing a solution of 97 parts ofpolymethyl methacrylate and 3 parts of the dye (22) in 300 parts ofchloroform, casting the solution on a glass substrate, and drying thecast layer of the solution.

The color filter produced as described above had a clear magenta colortone showing no sign of turbidity and diffusing a sensation oftransparency. When it was tested for lightfastness by the use of a xenonlamp lightfastness tester (produced by Heraeus Corp. and marketed undertrademark designation of "SUNTEST CPS") (black panel temperature 63°C.), it showed absolutely no sign of change in color tone. This factindicates that this color filter possessed ideal lightfastness.

EXAMPLE 130

A color filter was produced by faithfully following the procedure ofExample 129 excepting the dye (139) was used in place of the dye (22).

The color filter produced as described above had a clear cyanogen colortone showing no sign of turbidity and diffusing a sensation oftransparency. When it was tested for lightfastness by the use of a xenonlamp lightfastness tester (produced by Heraeus Corp. and marketed undertrademark designation of "SUNTEST CPS") (black panel temperature 63°C.), it showed absolutely no sign of change in color tone. This factindicates that this color filter possessed ideal lightfastness.

As described above, the novel compound of this invention is enabled toeffect control of an absorption wavelength properly for an intendedapplication within an absorption wavelength in the range of 480 nm to850 nm and acquire outstanding solubility in organic solvents byintroducing mainly secondary amino groups into one to four of the 5, 6,7, and 8 positions and to at least either the 6 or 7 position of thequinizarin structure. Further, since the lightfastness inherentlypossessed by the quinizarin structure can be maintained owing to thesubstituents at specific positions as compared with the conventionalquinizarin type dyes, this novel compound can be used as a visibleabsorption dye or a near infrared absorption dye in the field in whichthe dyes of the conventional development have proved to beimpracticable.

The toner of this invention is characterized by its high transparencyand, therefore, produces color images which excel in repeatability ofcolor and exhibit an ideal color tone and manifest prominentlightfastness. Even in continuous copying, it produces stable images atall times.

Further, the quinizarin type dye to be used in the construction of acyan and/or magenta type thermal-transfer sheet according to thisinvention exhibits highly satisfactory solubility in the solvents andbinder resins of the type intended for dyes, manifests an excellentcolor tone of the cyan and/or magenta color and, have excellentproperties useful for magenta color or cyan color when used in athermal-transferdye.

Since the novel quinizarin compound of this invention excels inabsorption characteristics, solubility, lightfastness, reflectance,sensitivity, and economy, it can manifest an outstanding effect when itis used in a tracing type optical recording medium which showsinterchangeability and convertibility among the players of CD, PHOTO-CD,and CD-ROM, i.e. devices which are in need of such characteristics asmentioned above.

Further, the use of the novel quinizarin compound of this inventionpermits production of a color filter which excels in lightfastness,avoids inducing turbidity, diffuses a sensation of transparency, andenjoys prominence of color tone. The use of the quinizarin compound ofthis invention also allows production of prints with excellent contrastand production of an ink jet grade ink composition capable of producingrecorded images excellent in lightfastness and color tone as well.

What is claimed is:
 1. A quinizarin compound which has a quinizarinstructure represented by a following formula (1) ##STR8## wherein one tothree of the 5, 6, 7, and 8 positions and at least either the 6 or 7position of the quinizarin structure are formed of secondary aminogroups and the remaining positions thereof are formed of at least onemember selected from the class consisting of hydrogen atom, halogenatoms, alkoxy groups, substituted and unsubstituted phenoxy groups,alkylthio groups, and substituted and unsubstituted phenylthio groups.2. A magenta dye comprising the quinizarin compound of claim 1containing one secondary amino group.
 3. A cyan dye comprising thequinizarin compound of claim 1 containing two secondary amino groups. 4.An electrophotographic grade color toner composition comprising at leastone coloring agent selected from the group consisting of the magenta dyecomprising a quinizarin compound of claim 1 containing one secondaryamino group and the cyan dye comprising the quinizarin compound of claim2 containing two secondary amino groups.
 5. A thermal-transfer recordingsheet characterized by possessing a coloring material layer containingat least one dye selected from the group consisting of the magenta dyecomprising a quinizarin compound of claim 1 containing one secondaryamino group and the cyan dye comprising the quinizarin compound of claim2 containing two secondary amino groups on a substrate.
 6. An opticalrecording medium having the quinizarin compound of claim 1 contained ina recording layer formed on a substrate.
 7. An ink jet grade inkcomposition comprising at least one dye selected from the groupconsisting of the magenta dye comprising a quinizarin compound of claim1 containing one secondary amino group and the cyan dye comprising thequinizarin compound of claim 1 containing two secondary amino groups anda vehicle.
 8. An ink jet grade ink composition according to claim 7,wherein said vehicle contains wax.
 9. A color filter containing thequinizarin compound of claim 1 in a filter substrate.
 10. A color filtercontaining at least one dye selected from the group consisting of themagenta dye comprising a quinizarin compound of claim 1 containing onesecondary amino group and the cyan dye comprising the quinizarincompound of claim 1 containing two secondary amino groups in a filtersubstrate.
 11. A method for the production of the quinizarin compound ofclaim 1, which comprises causing a quinizarin compound which has aquinizarin structure having one to four of the 5, 6, 7, and 8 positionsand at least either the 6 or 7 position formed of a halogen atom toreact with at least one member selected from the class consisting ofprimary amine compounds, aliphatic mercapto compounds, unsubstituted andsubstituted phenylthiols, ammonia, water, aliphatic hydroxy compounds,unsubstituted and substituted phenols.
 12. A method for the productionof the quinizarin compound set forth in claim 1, characterized bycausing a phthalic anhydride derivative which has a phthalic anhydridestructure having one to four of the 3, 4, 5, and 6 positions and atleast either the 4 or 5 position formed of at least one member selectedfrom the class consisting of secondary amino groups, alkylthio groups,and optionally substituted phenylthio groups and having the remainingpositions formed of at least one member selected from the classconsisting of hydrogen atom, halogen atoms, amino group, hydroxy group,alkoxy groups, and optionally substituted phenoxy groups to react withhydroquinone or 1,4-dimethoxybenzene.